Photocatalyzed Transition-Metal-Free Oxidative Cross ...

doi.org/10.26434/chemrxiv.13005509.v1

Photocatalyzed Transition-Metal-Free Oxidative Cross-CouplingReactions of TetraorganoboratesArif Music, Andreas N. Baumann, Florian Boser, Nicolas Müller, Florian Matz, Thomas C. Jagau, DorianDidier

Submitted date: 25/09/2020 • Posted date: 25/09/2020Licence: CC BY-NC-ND 4.0Citation information: Music, Arif; Baumann, Andreas N.; Boser, Florian; Müller, Nicolas; Matz, Florian; Jagau,Thomas C.; et al. (2020): Photocatalyzed Transition-Metal-Free Oxidative Cross-Coupling Reactions ofTetraorganoborates. ChemRxiv. Preprint. https://doi.org/10.26434/chemrxiv.13005509.v1

Readily accessible tetraorganoborate salts undergo selective coupling reactions under blue light irradiation inthe presence of catalytic amounts of transition-metal-free acridinium and rhodamine photocatalysts to furnishunsymmetrical biaryls, heterobiaryls and arylated olefins. This represents an interesting conceptual approachto forge C-C bonds between aryl, heteroaryl and alkenyl groups under smooth photochemical conditions.Computational studies were conducted to investigate the mechanism of the transformation.

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1

Photocatalyzed Transition-Metal-Free Oxidative Cross-Coupling

Reactions of Tetraorganoborates

Arif Music,[a] Andreas N. Baumann,[a] Florian Boser,[a] Nicolas Müller,[a] Florian Matz,[b] Thomas C.

Jagau[b] and Dorian Didier*[a]

[a] Dr. A. Music, Dr. A. N. Baumann, B.Sc. F. Boser, Dr. D. Didier

Ludwig-Maximilians University, Department of Chemistry

Butenandtstraße 5-13

81377 Munich, Germany

E-mail: [email protected]

[b] B.Sc. F. Matz, Prof. T. C. Jagau

KU Leuven, Quantum Chemistry and Physical Chemistry Section

Celestijnenlaan 200f - box 2404

3001 Leuven, Belgium

Abstract: Readily accessible tetraorganoborate salts undergo selective coupling reactions under blue light irradiation in the presence of catalytic

amounts of transition-metal-free acridinium and rhodamine photocatalysts to furnish unsymmetrical biaryls, heterobiaryls and arylated olefins.

This represents an interesting conceptual approach to forge C-C bonds between aryl, heteroaryl and alkenyl groups under smooth

photochemical conditions. Computational studies were conducted to investigate the mechanism of the transformation.

Biaryl derivatives constitute an essential class of compounds for

the development of pharmaceuticals and organic materials.[1] The

use of transition metal catalysis to forge C-C bonds between two

aryls has become inevitable, following the pivotal groundwork laid

by Corriu-Kumada-Tamao,[2] Negishi,[3] Suzuki-Miyaura[4] and

Stille[5] in the 1970’s. Although these traditional methods dominate

the world of cross-coupling reactions, modern synthetic planning

also includes direct C-H functionalization[6] and decarboxylative

strategies.[7] Besides, efforts have been made towards

transition-metal-free alternatives using borates as templates for

intramolecular biaryl formation. Few methods depict

homocoupling reactions using chemical oxidants such as

VO(OEt)Cl2,[8] iridium[9] and zinc complexes[10] (Scheme 1A).

Pioneered by Geske in 1959,[11] the formation of symmetrical

biaryls under electrochemical oxidation was extended to

fluorinated substrates by Waldvogel in 2018.[12] However, the

intramolecular coupling of borate salts was restrained to

homocoupling products until very recently (Scheme 1B). Building

on methodologies developed in our group to access

functionalized organoboron derivatives, we recently

demonstrated an efficient and chemoselective electrochemical

synthesis of unsymmetrical biaryls[13] and (hetero)-arylated

olefins[14] from readily accessible tetraorganoborate salts (TOBs).

The group of Studer similarly reported an elegant chemical

oxidation of unsymmetrical tetraorganoborates towards hetero-

biaryls using Bobbitt’s salt.[15]

The renaissance of photochemistry in past decades stems mainly

from the advantageous features it presents and the reactivity it

promotes in comparison with classical chemical processes.[16]

Photoredox catalysis is a rapidly expanding field as it offers a

tunable control over oxidation and/or reduction steps for the

generation of desired reactive intermediates.[17]

Only few examples have been reported on the formation of C-C

bonds between two aryl moieties through photoredox catalysis.

The groups of Sanford, Duan and König employed either

transition-metal photocatalysts ([Ru][18] or [Zn]-PDI[19] complexes),

or organophotocatalysts (Eosin Y or PDI)[20] to reduce diazo-

compounds and electron-poor aryl bromides under photo-

irradiation towards intermolecular aryl-aryl bond formation.

Scheme 1. Previous and present contributions to coupling reactions of TOBs.

The only example of photochemical borate rearrangement was

described by Doty in 1971. Rose Bengal was employed under UV-

light irradiation for the formation of biphenyl (Scheme 1C) from

NaBPh4 through oxygen-relayed electron transfer.[21] The authors

mailto:[email protected]

2

proposed that singlet oxygen is generated in situ, serving as the

oxidizing species in the transformation.

Herein, we present a conceptual hetero-coupling approach

towards functionalized biaryls and arylated olefins by harvesting

the potential of visible light photoredox catalysis to promote the

oxidation step needed to trigger the key C-C bond formation.

Table 1. Optimization of the photo-coupling reaction.

Photocatalyst Deviation from conditions Conversion[a]

(Isolated yield)

Rhodamine 6G Cl3CBr instead of O2, = 530 nm 45%

Acr-1 without O2 57% (50%)

Acr-1 none 85% (77%)

Acr-1 EtOH instead of MeCN, 8 days 69%

Acr-2 none 82%

Acr-3 none 83%

Acr-4 none 85% (78%)

Acr-1 5 mol% catalyst loading 85% (78%)

Acr-1 5 mol% cat., 50 °C, 16h[b] 91% (83%)

[a] Conversions determined by GC using n-undecane as internal standard. [b]

Changing the reaction setup induces a temperature increase to 50 °C (self-

heating), which allowed to decrease the reaction time to 16h, see SI.

Conditions were first optimized using unsymmetrical

tetraarylborate salt 1a. Rhodamine 6G and acridinium-based

photocatalysts (Acr)[22] were tested in the presence of Cl3CBr or

oxygen as oxidant, respectively (Table 1). While rhodamine 6G

only gave the desired product 2a in 45% conversion within 48h

under green light irradiation ( = 530 nm), Acr-1 allowed for its

formation in 57% without oxidant (50% isolated yield). In the

presence of oxygen, the conversion went up to 85% and

modifying the substitution pattern of the photocatalyst (Acr-2 to

Acr-4) gave similar results (82 to 85% conversion). Switching the

solvent to ethanol proved less efficient (69% conversion within 8

days). However, decreasing the catalyst loading to 5 mol% did not

alter the rate of coupling reaction, furnishing 2a in 78% yield after

48h under blue light irradiation ( = 470 nm). Using a more

powerful setup (13 W/cell)[23] allowed to decrease reaction times

to 16h, which also caused an increase in temperature to 50 °C.

Importantly, no traces of intermolecular coupling products were

detected in all cases.

We previously demonstrated that the first oxidation of a TOB salt

preferentially occurs on the most electron rich unsaturated

moiety.[13,14] As a logical consequence, structures 1 were

designed to possess one electron-richer aryl group (Ar1),

surrounded by electron-poorer groups (Ar2). With optimized

conditions and setup in hands, we started evaluating the scope of

the aryl-aryl photocoupling (Scheme 2). Worthy of note,

tetraarylborate salts were accessed ex-situ by reaction of an

aryltrifluoroborate species with the appropriate Grignard (or zinc)

reagent and were engaged further without purification. The yields

in Scheme 2 are therefore given for the two-step sequence. In the

presence of Acr-1 under blue light irradiation, we were able to

push the conversion to its maximum for the formation of biphenyl

2b (91%), showing great improvement in comparison with the

conditions previously described by the group of Doty (75% under

UV irradiation). Varying the substitution pattern of Ar1 by

introducing methyl, trimethylsilyl and ether moieties led to

structures 2c-j in good to excellent yields (up to 92%). Scaling up

the reaction to 3 mmol also gave 2h in a reasonable yield (77%).

Interestingly, these conditions allowed for an efficient coupling of

unprotected phenol derivatives 2k-l in up to 83% isolated yield,

verifying the functional group tolerance of the method. Amides

and nitriles also proved tolerable (2m-n), although lower yields

were obtained (47 to 53%). This can be attributed to the lower

reactivity of organozinc reagents (necessary for the tolerance of

amides and nitriles) towards starting trifluoroborates in the initial

formation of TOB salts. Electron-rich heteroaryls such as

benzoxadiazole and benzofurans were successfully coupled,

yielding compounds 2o-r (up to 70%). The transformation of

electron-poor pyridyl and quinolyl TOB derivatives proved more

difficult to achieve and compounds 2s-t were only isolated in up

to 56% yields. However, the presence of dibenzofurans as Ar2

groups led to 78% of coupling product (2u). Functionalization of

the pharmacologically relevant celecoxib structure gave 2v in

38% yield. The photocoupling reaction of sensitive halogenated

and pseudo-halogenated scaffolds was examined next, as they

open the possibility for further functionalization. While classical

cross-coupling methods usually give complex mixtures of

products through uncontrolled oxidative additions,[24] we have

previously demonstrated that an electrochemical process can be

employed to gain control over the formation of desired

functionalized compounds.[13] Remarkably, iodinated and

brominated substrates were tolerated under our photocatalyzed

conditions, furnishing halogenated biaryls 2w-2z in up to 69%

yield. Nitrile-substituted trifluoroborate substrates were also used

in this two-step sequence, leading to structures 2aa-ab in

moderate yields (47 to 63%).

3

Scheme 2. Scope of the photo-coupling of TOBs. [a] Borate salts were generated in-situ from the corresponding organotrifluoroborates and organomagesium species. [b] Yields are given over two steps, see SI. [c] Photocoupling was conducted on pure, isolated salts. [d] Prepared from organozinc reagents.

Having supported the proof of concept for photocoupling

reactions with a broad scope of biaryl products, we set out to

examine olefinations under similar conditions, as those would

provide an interesting alternative for the formation of styryl

derivatives. Model substrate 3a was employed for optimizations,

assuming that the oxidation of the alkenyl substituent would be

preferred over the remaining aryl groups.[14] Performing the

reaction with 5 mol% of Acr-1 without oxidant afforded 4a in 35%

yield and similar conditions to the ones used for biaryl formation

only pushed the conversion to 65% (Table 2).

Table 2. Optimization of the photo-olefination reaction.

oxidant Conversion[a]

(Isolated yield) oxidant

Conversion[a]

(Isolated yield)

O2 65% (<10%)[b] PhSSPh 57% (40%)

none 45% (35%) K2HPO4 73% (57%)

4

[a] Conversions determined by GC.[b] The epoxide 5a (from 4a) was isolated, see

Scheme 3.

However, the main product was found to be the overoxidized

epoxide 5a (see Scheme 3). Diphenyldisulfide did not improve the

conversion of 3a, and dipotassium phosphate furnished 4a in 57%

isolated yield (73% conversion of 3a). These last conditions (cond.

A, Scheme 3A) were therefore used in the exploration of the

reaction scope. -styryl moieties were evaluated first, providing

(E)-bisarylated olefins 4a-e with up to 57% yield. Interestingly,

engaging (E)- alkenyl substrates led to the stereospecific

formation of products (E)-4 under thermodynamic control. Cyclic

olefins 4f-j were synthesized next, although conversions were

generally lower than for acyclic ones, with the exception of 4i

(69% isolated yield). When oxygen was used instead of K2HPO4,

trans-epoxides 5a and 5b were formed in up to 54% yield.

Scheme 3. Photo-olefination of alkenylborates. [a] Borate salts were generated in-situ from the corresponding organotrifluoroborates. [b] Yields are given over two steps, see SI. [c] Photocoupling was conducted on pure, isolated salts.

More than adding synthetic interest to the method, these findings

indicate that the oxidant plays an essential role in the

transformation and its associated catalytic cycle. In contrast to the

work from Doty, our different set of conditions leads us to believe

that oxygen plays a role in the re-oxidation of the catalyst, rather

than in the oxidation of the substrate itself.

We therefore propose a reaction mechanism in which the oxygen

is implicated as the oxidant that enables the catalyst regeneration

(Scheme 4). Blue light irradiation (470 nm) allows for the

acridinium to reach its active, excited state to abstract an electron

from substrate 1a. The resulting oxidized species [1a.] undergoes

a pseudo 1,2-metallate rearrangement,[13,14] giving the cyclic

intermediate 6, which further opens towards 7 through [TS]#.

Oxygen further intervenes to regenerate the photocatalyst from its

reduced form, producing [O2].-.[25] As witnessed in the reaction of

alkenyl derivatives, we know that oxygen interacts with the

intermediates to produce the corresponding epoxides. In

consequence, we advance that an active oxygen species reacts

with [7] to promote an elimination reaction towards the formation

of 2a.

Scheme 4. Theoretical studies and proposed mechanism.

To assess a plausible reaction path, we performed a series of

density functional theory calculations on 1a using the software Q-

Chem[26] with the B3LYP functional[27] and the 6-31G* basis set.

Here we determined equilibrium structures and computed the

Gibbs free energies for the initial anion 1a and radical [1a.] as well

as for the radicals 6 and 7. We found a transition state between 6

5

and 7 at a barrier height of 50 kJ·mol-1 as depicted in Scheme 4.

This completes the picture of the reaction mechanism: the

oxidation of the anion is followed by a relaxation during which the

reacting six-membered rings rotate to face each other, therefore

coming closer together. The C-B-C-angle of 108° in the anion

changes to 87° in 6. This structure has CS symmetry when

rotationally averaging over the atomic positions of the methoxy

group. During the reaction, the B-C bond is cleaved in the same

time that the C-C bond. The CS symmetry is maintained while the

bond breaks and lowered only afterwards. The C-B-C-angle in the

transition state is 60° and shrinks further while the tetrahedral

coordination at the carbon atom in the oxidized ring is restored.

In summary, we have demonstrated the feasibility of a

chemoselective coupling of tetraorganoborates using organo-

photocatalysis. This conceptual approach has allowed us to

access a wide range of biaryl, heterobiaryl and olefin products

under blue light irradiation, in a simple and practical setup. A

deeper analysis of the mechanism through experimental and

theoretical studies led us to propose an unusual reaction path that

goes through a cyclic intermediate, essential to the formation of

the C-C bond. Heterocoupling reactions were achieved and we

are currently working on alternative borate salts with increased

sustainability and atom economy. There is no doubt that these

advances within the field of photocatalysis will enable the

discovery of new reactions in the near future.

Acknowledgements

D.D., A.M and A.N.B. are grateful to the Fonds der Chemischen

Industrie, the Deutsche Forschungsgemeinschaft (DFG grants: DI

2227/2-1 and DI2227/4-1), the SFB749 and the Ludwig-

Maximilians University for PhD funding and financial support. F.M.

is grateful to the European Union for co-funding by the Erasmus+

program. T.C.J. gratefully acknowledges funding from the

European Research Council (ERC) under the European Union’s

Horizon 2020 research and innovation program (Grant

Agreement No. 851766). Prof. Christof Sparr and his group are

kindly acknowledged for supplying some of the acridinium

photocatalysts used in this project.

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1

Photocatalyzed Transition-Metal-Free Oxidative Cross-Coupling Reactions of

Tetraorganoborates

Arif Music[a], Andreas N. Baumann[a], Florian Boser[a], Nicolas Müller[a], Florian Matz[b],

Thomas C. Jagau[b] and Dorian Didier*[a]

[a]Department Chemie,

Ludwig-Maximilians-Universität

Butenandtstraße 5-13, D-81377 Munich

[email protected]

[b]KU Leuven, Quantum Chemistry and Physical Chemistry Section

Celestijnenlaan 200f - box 2404

3001 Leuven, Belgium

Supporting Information

1. General Considerations 2

2. Experimental Procedures and Data 3

3. NMR Spectra 30

4. Calculations 71

5. Additional LED information 77

mailto:[email protected]

2

1. General Considerations

Commercially available starting materials such as bromides and potassium aryl trifluoroborate

salts were used without further purification unless otherwise stated. All reactions were carried

out under N2 atmosphere in flame-dried glassware unless otherwise stated. Syringes, which

were used to transfer anhydrous solvents or reagents, were purged with nitrogen prior to use.

THF was refluxed and distilled from sodium benzophenone ketyl under nitrogen. Et2O was

predried over CaCl2 and passed through activated Al2O3 (the solvent purification system SPS-

400-2 from Innovative Technologies Inc.). MeCN was purchased in HPLC gradient grade

(>=99.9%) from Fisher Scientific.

Chromatography purifications were performed using silica gel (SiO2, 0.040-0.063 mm, 230-

400 mesh ASTM) from Merck. The spots were visualized under UV (254 nm) or by staining the

TLC plate with either KMnO4 solution (K2CO3, 10 g – KMnO4, 1.5 g – H2O, 150 ml – NaOH

10% in H2O, 1.25 ml) or p-anisaldehyde solution (conc. H2SO4, 10 ml – EtOH, 200 ml – AcOH,

3 ml – p-anisaldehyde, 4 ml). Yields refer to isolated yields of compounds estimated to be

>95% pure as determined by 1H NMR and GC-analysis. The 13C and 1H NMR spectra were

recorded on VARIAN Mercury 200, BRUKER ARX 300, VARIAN VXR 400 S and BRUKER

AMX 600 instruments. Chemical shifts are reported as δ values in ppm relative to the residual

solvent peak (1H-NMR, 13C-NMR) in deuterated chloroform (CDCl3: δ 7.26 ppm for 1H-NMR

and δ 77.16 ppm for 13C-NMR), deuterated acetonitrile (CD3CN: δ 1.94 ppm for 1H-NMR and

δ 118.69 and 1.39 ppm for 13C-NMR) or deuterated DMSO (DMSO-d6: δ 2.50 ppm for 1H-NMR

and δ 39.51 ppm for 13C-NMR). Abbreviations for signal coupling are as follows: s (singlet), d

(doublet), t (triplet), q (quartet), quint (quintet), m (multiplet) and br (broad). Reaction endpoints

were determined by GC monitoring of the reactions with n-undecane as an internal standard.

Gas chromatography was performed with machines of Agilent Technologies 7890, using a

column of type HP 5 (Agilent 5% phenylmethylpolysiloxane; length: 15 m; diameter: 0.25 mm;

film thickness: 0.25 μm) or Hewlett-Packard 6890 or 5890 series II, using a column of type HP

5 (Hewlett-Packard, 5% phenylmethylpolysiloxane; length: 15 m; diameter: 0.25 mm; film

thickness: 0.25 μm). High resolution mass spectra (HRMS) and low-resolution mass spectra

(LRMS) were recorded on Finnigan MAT 95Q, Finnigan MAT 90 instrument or JEOL JMS-700.

Infrared spectra were recorded on a Perkin 281 IR spectrometer and samples were measured

neat (ATR, Smiths Detection DuraSample IR II Diamond ATR). The absorption bands were

reported in wave numbers (cm-1) and abbreviations for intensity are as follows: vs (very strong;

maximum intensity), s (strong; above 75% of max. intensity), m (medium; from 50% to 75% of

max. intensity), w (weak; below 50% of max. intensity) and br (broad). Melting points were

determined on a Büchi B-540 apparatus and are uncorrected.

n-BuLi was purchased as a solution in cyclohexane/hexanes mixtures from Rockwood Lithium

GmbH. The concentration of organometallic reagent from commercially purchased and

3

synthesized reagents was determined either by titration of isopropyl alcohol using the indicator

1,10-phenanthroline or by titration of N-benzylbenzamide in THF for organolithium reagents.

Aryl Grignard reagents and Arylzinc reagents were titrated using iodine in THF at room

temperature.

2. Experimental Section

Abbreviations: TAB salt TetraArylBorate salt

ATB salt AlkenylTriarylBorate salt

2.1 Initial Test of Theory for the Biaryl-Coupling of TAB Salts

The first photoredox catalyzed oxidation of TAB salt 1a was accomplished by using Rhodamine

6G and CCl3Br as an oxidant. This led to the moderate yield of 45% after 48 h in MeCN under

green light.

In a second reaction procedure the photocatalyst was replaced by the acridinium-based

photocatalyst Acri-1 (see 2.2 Overview of used Photocatalysts). This led to the product

formation in 50% yield after 48 h using blue light.

According to these initial results, the chapter “2.3 Optimizations” describes the consecutive

optimization of this transformation by means of Setup, Oxidant, Catalyst and Solvent.

4

2.2 Overview of used Photocatalysts

Figure S1 – Used photocatalysts for the transformation of TAB/ATB salts into biaryls and functionalized

alkenes.

Acridinium catalysts Acri-1 and Acri-2 as well as Rhodamine 6G were obtained from Sigma-

Aldrich. The Sparr group is gratefully acknowledged for supplying Acri-3, Acri-4 and Acri-5.1

2.3 Optimization of the Photoredox oxidation of TAB Salts

For all following optimizations the test salt potassium tris(4-fluorophenyl)(4-

methoxyphenyl)borate (1a) was used, which was synthesized via general procedure E (see

section 2.6 General Procedures). Furthermore, the commercially available acridinium-based

photocatalyst Acri-1 was applied for most of the optimizations for biaryl couplings.

A: Setup

Initially, the illumination of the samples by means of a simple LED light band was arranged in

a circle at a distance of about 3 cm (setup 1, Figure S2, A) from the outermost point of six

reaction vessels.

1 a) B. Zilate, C. Fischer, C. Sparr, Chem. Commun. 2020, 56, 1767–1775; b) C. Fischer, C. Kerzig, B. Zilate, O. S. Wenger, C. Sparr, ACS Catal. 2020, 10, 210–215.

5

Figure S2 – Photochemical setups 1 (A), 2 (B) and 3 (C+D) with used reaction vessel (E).

By placing the LED light band directly around the reaction vessel, the distance is minimized to

about 0.1 cm, directly intensifying and increasing light penetration (setup 2, Figure S2, B).

Further improvements were achieved using more powerful LED setups with thin-walled

glassware (setup 3, array of 16 LEDs, Figure S2, C to E) to ensure maximum light penetration.

The improvement in reaction setup is confirmed by the product formation values on GC-

analysis relative to the internal standard n-undecane (see Table S1).

Table S1 – Time course of product conversion in different reaction setups relative to the internal standard

n-undecane.

Setup Time 16h 24h 48h 72h Isolated yield

Setup 1 n.d 64% 72% 75% 69 Setup 2 n.d 83% 85% 86% 77 Setup 3 91% 91% n.d. n.d. 83

The reaction proceeds much faster and with greater conversion when a single reaction vessel

is directly irradiated and when stronger LED setups are used (total power consumption approx.

13 W). LEDs from the company RND components were used for setup 3 (Part No. RND 135-

00178)2. While the reactions in setups 1 and 2 reach temperatures of 30 °C, the heat generated

2 Additional information can be found in chapter 5 of this SI.

A

B D

C E

6

from the RND LEDs (PCE of 95%) causes the reaction to heat to 50 °C, which did not cause

any problems for other substrates. Additionally, the reaction time could be reduced to 16h and

setup 3 was therefore used as the ideal photochemical setup for scope analysis.

B: Oxidant

For the regeneration of the acridinium-based photocatalyst an oxidant like O2 is used and was

therefore tested. A O2-ballon was used and the normal atmosphere in the tube was exchanged

by O2 via bubbling into the MeCN solution. An increased yield was detected and the conversion

after 48 h was greatly enhanced.

Table S2 – Regeneration of acridinium-based photocatalyst by using O2 as oxidant relative to the internal

standard n-undecane.

Oxidant Time Conv. Isolated yield

- 48 h 57% 50% O2 48 h 73% 63%

C: Solvent

Table S3 – Time course of product conversion in different solvents using setup 1 relative to the internal

standard n-undecane.

Solvent Time 24 h 48 h 72 h 4 d 6 d 8 d

MeCN 64% 74% 75% unchanged unchanged unchanged EtOH 12% 30% n.d. 48% 55% 69%

D: Photocatalyst

The comparison of conversion rates from different acridinium-based photocatalysts Acri-1 to

Acri-5 clearly shows similar performances regarding conversion time and yields. Even though

the best results were observed for Acri-5, we decided to use Acri-1 as our standard

photocatalyst, as the catalyst has the advantages of commercial availability and lower cost

compared to Acri-5.

7

Table S4 – Time course of product conversion using different photocatalysts relative to the internal standard n-undecane.

Catalyst Time 24 h 48 h Isolated Yield

Acri-1 83% 85% 77% Acri-2 82% 82% n.d. Acri-3 78% 83% n.d. Acri-4 83% 85% 78% Acri-5 83% 84% 81%

E: Catalyst Loading

Table S5 – product conversion and yield after 48 h using different catalyst loading of Acri-1 relative to the internal standard n-undecane.

Cat. Loading Time 48 h Isolated Yield

15 mol% 86% 79% 10 mol% 84% 76% 5 mol% 85% 78%

2.5 mol% 80% 70%

Within the scope of the measurement inaccuracy a catalyst loading of 5 mol% shows the

best results regarding reaction speed, yield and atom-economy.

F: Summary of Optimizations

Taking all measured results into account, we decided to use the following conditions for the

oxidation of TAB salts for the scope synthesis of biaryl products. Test substrate 1a yielded the

desired biaryl compound 2a in 83% yield.

8

2.4 Initial Test of Theory for the Alkenyl-Aryl-Coupling of ATB Salts

Based on our optimized photocatalyzed oxidation of TAB salts, the same conditions were

initially applied for the conversion of ATB salts like potassium (E)-tris(4-

fluorophenyl)(styryl)borate 3a. However, as a result of the necessity of O2 as an oxidant for the

recovery of the acridinium-based catalyst, the trans-epoxide 5a was obtained in moderate

yield.

2.5 Optimization of the Photooxidation of ATB Salts

For all following optimizations the test salt potassium (E)-tris(4-fluorophenyl)(styryl)borate (3a)

was used, which was synthesized by general procedure F (see section 2.6 General

Procedures).

A: Oxidant

Table S6 – Optimization for olefination reactions.

Oxidant Time Conv. Isolated yield

- 48h 45% 35% O2 48h 65% <10% (epoxide)

PhSSPh 48h 57% 40% K2HPO4 48h 73% 57%

9

As an O2 atmosphere was found to cause selective epoxide formation, other milder oxidants

were screened. Optimal results were found for K2HPO4 (trihydrate), which gave the desired

olefinated arene 4c in 57% yield.

2.6 General Procedures

A: Synthesis of Aryl Grignard Reagents

A Schlenk flask was charged with magnesium turnings (972 mg, 40 mmol, 1.6 equiv.) and

dried in vacuo using a heat gun (600 °C, 2 x 5 min). After addition of THF (2.0 mL) and 1,2-

dibromoethane (2 drops), the mixture was heated to boil with a heat gun to activate the

magnesium. The corresponding aryl bromide (25 mmol, 1.0 equiv.) was dissolved in THF

(23.0 mL for approximately 1 M solution or 48 ml for 0.5 M solution) and added to the activated

magnesium suspension dropwise. After completion of the addition, the mixture was stirred for

one hour at room temperature to yield a THF-solution of the arylmagnesium reagents.

B: Synthesis of Arylzinc Reagents

According to a previously reported procedure,3 a Schlenk flask was charged with lithium

chloride (212 mg, 5 mmol, 1.0 equiv.) and dried in vacuo using a heat gun (500 °C, 2 x 5 min).

Zinc powder (490 mg, 7.5 mmol, 1.5 equiv.) was added and the flask was dried again in vacuo

(350 °C, 2 x 5 min). After addition of THF (5.0 mL), 1,2-dibromoethane (2 drops) and TMS-Cl

(5 drops), the mixture was heated to boil with a heat gun to activate the zinc. The corresponding

aryl iodide (5 mmol, 1.0 equiv.) was added neat to the activated zinc suspension at room

temperature and the reaction was stirred at 50°C until complete consumption of the aryl iodide

was observed by GC analysis.

3 A. Krasovskiy; V. Malakhov; A. Gavryushin; P. Knochel, Angew. Chem. Int. Ed. 2006, 118, 6186-6190.

10

C: Preparation of Aryl Boronic Acids starting from Aryl Bromides

Adapted from a previously reported procedure,4 commercial available aryl bromides (5.0 mmol,

1.0 equiv.) were dissolved in 20 mL of THF and cooled to -78 °C. n-BuLi (5.5 mmol, 2.43 M,

1.1 equiv.) was added dropwise and the reaction stirred for 30 minutes. B(Oi-Pr)3 was then

added dropwise (10 mmol, 2.0 equiv.) and the reaction stirred for further 30 minutes. The

reaction was then allowed to reach 0 °C and was stirred at that temperature for one hour. The

reaction was then quenched with 1 M HCl (40 mL) and extracted with EtOAc (3 x 50 mL). The

combined organic phases were dried over MgSO4, filtered and concentrated under reduced

pressure. The crude product was used without further purification in General Procedure D.

D: Preparation of Potassium Trifluoroborate Salts starting from Aryl Boronic Esters and

Acids

Adapted from a previously reported procedure,2 5.0 mmol (1.0 equiv.) of commercially

available Aryl boronpinacol esters, boronic acids or crude intermediates from General

Procedure C were dissolved in 15 mL of a 4:1 (v/v) mixture of MeOH and H2O. The mixture

was cooled to 0 °C and KHF2 (4.0 equiv.) was added neat. The mixture was vigorously stirred

at room temperature overnight and then concentrated under reduced pressure. The remaining

solids were extracted with boiling acetone (2 x 50 mL) and twice with acetone at room

temperature (2 x 50 mL). The acetone was removed under reduced pressure and the

remaining solid was dissolved in a minimum amount of boiling acetone, before being treated

with diethyl ether, which resulted in precipitation of a white solid. The solids were filtered,

washed with diethyl ether and dried in vacuo to yield potassium aryltrifluoroborate salts SM1−4.

(Note: A recrystallization in hexanes/acetone mixtures was performed in cases, where the

desired potassium trifluoroborate salt was not pure by 1H NMR.)

4 E.F. Santos-Filho; J. C. Sousa; N. M. M. Bezerra; P.H. Menezes, Tetrahedron Letters 2011, 52, 5288-5291.

11

E: Preparation of Test Salt Potassium tris(4-fluorophenyl)(4-methoxyphenyl)borate 1a

A 25 mL Schlenk flask was charged with trifluoro(4-methoxyphenyl)borate (3.0 mmol,

1.0 equiv.) and 6 mL of THF were added. The mixture was cooled to 0 °C and the desired aryl

Grignard reagent (9.45 mmol, 3.15 equiv.) was added dropwise over 30 minutes via syringe

pump. The reaction was allowed to warm to room temperature and was stirred one hour. The

reaction was then quenched with 5 mL of aqueous saturated K2CO3 solution and extracted

with EtOAc (3 x 40 mL). The combined organic phases were filtered and concentrated under

reduced pressure. The crude solid product was washed with cold diethyl or diisopropyl ether,

filtered and dried in vacuo to afford potassium tris(4-fluorophenyl)-(4-methoxyphenyl)borate

salt 1a (1.10 g, 2.49 mmol, 83%).5

F: Preparation of Test Salt Potassium (E)-tris(4-fluorophenyl)(styryl)borate 3a

A 25 mL Schlenk flask was charged with (E)-trifluoro(styryl)borate (3.0 mmol, 1.0 equiv.) and

6 mL of THF were added. The mixture was cooled to 0 °C and the desired aryl Grignard

reagent (9 mmol, 3 equiv.) was added dropwise over 30 minutes via syringe pump. The

reaction was allowed to warm to room temperature and was then quenched with 5 mL of

aqueous saturated K2CO3 solution and extracted with EtOAc (3 x 40 mL). The combined

organic phases were filtered and concentrated under reduced pressure. The crude solid

product was washed with cold diethyl or diisopropyl ether, filtered and dried in vacuo to afford

potassium (E)-tris(4-fluorophenyl)(styryl)borate salt 3a (2.47 mmol, 949 mg, 82%).6

5 A. Music, A. N. Baumann, P. Spieß, A. Plantefol, T.-C. Jagau, D. Didier, J. Am. Chem. Soc. 2020, 142, 9, 4341-4348. 6 A. N. Baumann, A. Music, J. Dechent, N. Müller, T. C. Jagau, D. Didier, Chem. Eur. J. 2020, 26, 8382–8387.

12

G: Two-pot Procedure for the Synthesis of (Hetero)Biaryls starting from Potassium

Aryltrifluoroborate Salts

A dry 25mL Schlenk flask was charged with the corresponding potassium trifluoroborate salt

(0.4 mmol, 1.0 equiv.) and 1.5 mL of THF was added under nitrogen. The mixture was cooled

to 0 °C and the corresponding organometallic reagent (1.26 mmol, 3.15 equiv.) was added

dropwise over 30 minutes via syringe pump. The reaction was allowed to warm to room

temperature and was stirred for two hours. The mixture was then quenched with 5 mL water

and extracted with EtOAc (3x40 mL). The combined organic phases were filtered and

concentrated under reduced pressure. The crude product was then dissolved in 8 mL of HPLC

grade MeCN (which contains traces of water) and transferred into a 25 mL reaction tube.

Photocatalyst 9-mesityl-10-methylacridinium tetrafluoroborate (Acri-1) (8 mg, 20 μmol,

0.05 equiv., 5 mol%) was added, the atmosphere was replaced with oxygen and the reaction

tube was directly irradiated under stirring with blue light (~460 nm) at 50°C for 16h.

Subsequently the solution was worked up by treating with water and extraction with diethyl

ether (3x15 mL). The combined organic phases were dried over MgSO4, filtered and

concentrated under reduced pressure. The crude product was purified by flash column

chromatography on silica gel yielding product 2a-ab.

Note that for products 2k and 2l 4.2 equiv. of the desired arylgrignard reagent (1.68 mmol)

were used due to deprotonation of the hydroxy group by one equivalent of Grignard reagent.

Additionally, Products 2a and 2b were directly synthesized from the pure potassium

tetraarylborate salt 1a and commercially available sodium tetraphenylborate. Epoxides 5a and

5b were also synthesized using general procedure G and the appropriate starting materials.

H: Two-pot Procedure for the synthesis of functionalized alkenes starting from

potassium alkenyl trifluoroborate salts

13

A dry 25mL Schlenk flask charged with the corresponding potassium trifluoroborate salt

(0.4 mmol, 1.0 equiv.) and 1.5 mL of THF was added under nitrogen. The mixture was cooled

to 0 °C and the corresponding organometallic reagent (1.2 mmol, 3.0 equiv.) was added

dropwise over 30 minutes via syringe pump. The reaction was allowed to warm to room

temperature and was stirred for two hours. The mixture was then quenched with 5 mL water

and extracted with EtOAc (3x40 mL). The combined organic phases were filtered and

concentrated under reduced pressure. The crude product was then dissolved in 8 mL of HPLC

grade MeCN (which contains traces of water) and transferred into a 25 mL reaction tube.

Photocatalyst 9-mesityl-10-methylacridinium tetrafluoroborate (Acri-1) (8 mg, 20 μmol,

0.05 equiv., 5 mol%) and 2 equiv. of K2HPO4 (0.8 mmol, 182 mg) was added, the atmosphere

was replaced with nitrogen and the reaction tube was directly irradiated under stirring with blue

light (~460 nm) at 50°C for 16h. Subsequently the solution was worked up by treating with

water and extraction with diethyl ether (3x15 mL). The combined organic phases were dried

over MgSO4, filtered and concentrated under reduced pressure. The crude product was

purified by flash column chromatography on silica gel yielding product 4a-j.

2.3 Experimental Data

Potassium trifluoro(4-(trimethylsilyl)phenyl)borate (SM1)

Using (4-(trimethylsilyl)phenyl)boronic acid according to general

procedure D (4.33 mmol scale), provided SM1 (4.26 mmol, 1.09 g, 98%)

as a white solid. 1H NMR (400 MHz, Acetonitrile-d3) δ 7.42 (d, J = 7.3 Hz,

2H), 7.35 (d, J = 6.3 Hz, 2H), 0.22 (s, 9H) ppm. 13C NMR (101 MHz, Acetonitrile-d3) δ 136.9,

132.6, 131.8, -1.0 ppm. HRMS (ESI-Quadrupole): m/z: calcd for C9H13BF3Si- [M-K]-: 217.0837;

found: 217.0835. Analytical data in accordance to literature.7

Potassium trifluoro(6-methoxynaphthalen-2-yl)borate (SM2)

Using 2-bromo-6-methoxynaphthalene according to general

procedure C (5.0 mmol scale), provided SM2 (3.97 mmol, 1.05 g,

79%) as a white solid. 1H NMR (400 MHz, Acetonitrile-d3) δ 7.82 (s,

1H), 7.69 (d, J = 8.9 Hz, 1H), 7.60 – 7.55 (m, 2H), 7.16 (d, J = 2.6 Hz, 1H), 7.02 (dd, J = 8.9,

2.6 Hz, 1H), 3.87 (s, 3H) ppm. 13C NMR (101 MHz, Acetonitrile-d3) δ 157.4, 134.4, 132.2, 130.5,

130.1, 129.8, 125.3, 117.9, 106.3, 55.7 ppm. HRMS (ESI-Quadrupole): m/z: calcd for

C11H9BF3O- [M-K]-: 225.0704; found: 225.0702. Analytical data in accordance to literature.8

7 N. M. Ellis; G. A. Molander, J. Org. Chem. 2006, 71, 7491−7493. 8 J. Lindh; J. Sävmarker; P. Nilsson; P. J. R. Sjöberg; M. Larhed, Chem. Eur. J. 2009, 15, 4630−4636.

14

Potassium trifluoro(2-methoxy-5-pyridinyl)borate (SM3)

Using 2-methoxypyridine-5-boronic acid according to general procedure

D (3.0 mmol scale), provided SM3 (1.84 mmol, 395 mg, 61%) as a white

solid. 1H NMR (400 MHz, Acetone-d6) δ 8.17 (s, 1H), 7.66 (dd, J = 8.1,

1.6 Hz, 1H), 6.51 (d, J = 8.1 Hz, 1H), 3.79 (s, 3H) ppm. 13C NMR (101 MHz, Acetone-d6) δ

163.4, 150.3, 143.2, 109.2, 52.7 ppm. HRMS (ESI-Quadrupole): m/z: calcd for C6H6BF3NO-

[M-K]-: 176.0500; found: 176.0499. Analytical data in accordance to literature.9

Potassium trifluoro(2-methylquinolin-6-yl)borate (SM4)

Using 6-bromo-2-methylquinoline according to general procedure C (5.0

mmol scale), provided SM4 (3.25 mmol, 810 mg, 65%) as a white solid.

1H NMR (400 MHz, Acetonitrile-d3) δ 8.11 (d, J = 8.3 Hz, 1H), 7.89 (s,

1H), 7.84 (d, J = 7.0 Hz, 1H), 7.74 (d, J = 7.3 Hz, 1H), 7.27 (d, J = 8.4 Hz, 1H), 2.65 (s, 3H)

ppm. 13C NMR (101 MHz, Acetonitrile-d3) δ 157.7, 147.4, 137.5, 135.3, 130.4, 127.0, 126.1,

121.8, 24.9 ppm. HRMS (ESI-Quadrupole): m/z: calcd for C10H8BF3N- [M-K]-: 210.0707; found:

210.0706. Analytical data in accordance to literature.3

Potassium trifluoro(4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)phenyl)borate

(SM5)

Using 1-(4-bromophenyl)-5-(p-tolyl)-3-(trifluoromethyl)-1H-

pyrazole according to general procedure C (9.5 mmol scale),

provided SM5 (7.35 mmol, 3.01 g, 77%) as a white solid. 1H NMR

(400 MHz, Acetonitrile-d3) δ 7.49 – 7.43 (m, 2H), 7.15 (s, 4H), 7.08

(d, J = 7.6 Hz, 2H), 6.85 (s, 1H), 2.32 (s, 3H) ppm. 13C NMR (101

MHz, Acetonitrile-d3) δ 145.9, 142.5 (q, J = 37.6 Hz), 140.0, 138.0, 132.8, 130.0, 129.7, 127.4,

124.8, 122.8 (d, J = 267.6 Hz), 105.6, 21.1 ppm. HRMS (ESI-Quadrupole): m/z: calcd for

C17H12BF6N2- [M-K]-: 369.1003; found: 369.1007. Analytical data in accordance to literature.3

Potassium trifluoro(4-iodophenyl)borate (SM6)

Using 1,4-diiodobenzene according to general procedure C (5 mmol scale),

provided SM6 (4.68 mmol, 1.45 g, 94%) as a white solid. 1H NMR (400 MHz,

Acetone-d6) δ 7.45 (d, J = 7.7 Hz, 2H), 7.27 (d, J = 7.7 Hz, 2H) ppm. 13C NMR

(101 MHz, Acetone-d6) δ 136.0, 135.0, 91.3 ppm. HRMS (ESI-Quadrupole): m/z: calcd for

C6H4BF3I- [M-K]-: 270.9408; found: 270.9411. Analytical data in accordance to literature.10

9 G. A. Molander, S. L. Trice, B. Tschaen, Tetrahedron 2015, 71, 5758–5764. 10 Q. I. Churches, J. F. Hooper, C. A. Hutton, J. Org. Chem. 2015, 80, 5428–5435.

15

Potassium tris(4-fluorophenyl)(4-methoxyphenyl)borate (1a)

Using potassium 4-methoxyphenyltrifluoroborate and 4-

fluorophenylmagnesium bromide according to general procedure E (3.0

mmol scale), provided 1a (2.49 mmol, 1.10 g, 83%) as a white solid. 1H NMR

(400 MHz, Acetonitrile-d3) δ 7.21 – 7.13 (m, 6H), 7.11 – 7.04 (m, 2H), 6.79

– 6.71 (m, 6H), 6.66 – 6.61 (m, 2H), 3.70 (s, 3H) ppm. 13C NMR (101 MHz,

Acetonitrile-d3) δ 161.9, 160.4 (d, J = 3.5 Hz), 159.9 (d, J = 3.3 Hz), 159.6,

159.4 (d, J = 3.3 Hz), 158.9 (d, J = 3.3 Hz), 156.7, 137.4 (ddd, J = 5.4, 3.3, 1.6 Hz), 137.0 (dd,

J = 3.4, 1.6 Hz), 112.8 (dd, J = 6.1, 3.0 Hz), 112.6 (dd, J = 6.1, 3.0 Hz), 112.4 (dd, J = 6.0, 2.9

Hz), 55.2 ppm. HRMS (ESI-Quadrupole): m/z: calcd for C25H19BF3O- [M-K]-: 403.1487; found:


Potassium (E)-tris(4-fluorophenyl)(styryl)borate (3a)

Using potassium (E)-trifluoro(styryl)borate and 4-fluorophenylmagnesium

bromide according to general procedure F (3.0 mmol scale), provided 3a

(2.61 mmol, 1.14 g, 87%) as colourless solid. 1H NMR (400 MHz,

(CD3)2CO) δ 7.59 (d, J = 17.8 Hz, 1H), 7.34 – 7.28 (m, 2H), 7.24 – 7.13 (m,

8H), 7.01 – 6.92 (m, 1H), 6.76 – 6.68 (m, 6H), 6.13 ppm (ddd, J = 17.8, 6.9,

3.3 Hz, 1H). 13C NMR (101 MHz, (CD3)2CO) δ 160.9 (d, J = 236.1 Hz), 160.1 (d, J = 3.4 Hz),

159.6 (d, J = 3.4 Hz), 159.1 (d, J = 4.0 Hz), 158.6 (d, J = 4.3 Hz), 158.0, 157.5, 143.7 (dd, J =

8.6, 4.3 Hz), 137.0 (ddd, J = 5.5, 3.5, 1.6 Hz), 131.6, 128.7, 126.0, 125.0, 112.5 ppm (ddd, J =

17.7, 6.1, 2.9 Hz). HRMS (ESI-Quadrupole): m/z: calcd for C26H19BF3- [M-K]-: 399.1532; found:


Potassium (E)-tris(phenyl)(styryl)borate (3b)

Using potassium (E)-trifluoro(styryl)borate and phenylmagnesium bromide

according to general procedure F, (3.0 mmol scale), provided 3b (2.47 mmol,

949 mg, 82%) as colourless powder. 1H NMR (400 MHz, (CD3)2CO) δ 7.71

(d, J = 17.8 Hz, 1H), 7.34 – 7.27 (m, 8H), 7.18 – 7.11 (m, 2H), 6.99 – 6.92 (m,

7H), 6.83 – 6.77 (m, 3H), 6.20 ppm (ddd, J = 17.8, 6.7, 3.3 Hz, 1H). 13C NMR (101 MHz,

(CD3)2CO) δ 165.5, 165.0, 164.5, 164.1, 160.4, 159.9, 159.4, 158.9, 144.2 (dd, J = 8.5, 4.1

Hz), 136.4 (dd, J = 2.9, 1.4 Hz), 131.2, 128.7, 126.2 (dd, J = 5.6, 2.7 Hz), 125.9, 124.6, 122.4

ppm. 11B NMR (128 MHz, CD3CN) δ -8.75 ppm. HRMS (ESI-Quadrupole): m/z: calcd for

C26H22B- [M-K]-: 345.1815; found: 345.1824. IR (Diamond-ATR, neat) 𝜈𝑚𝑎𝑥 (cm-1): 1742 (w),

1596 (w), 1578 (w), 1493 (w), 1477 (w), 1444 (w), 1428 (w), 1261 (w), 1236 (w), 1185 (w),

1152 (w), 1070 (w), 1030 (w), 1011 (w), 1006 (w), 958 (w), 912 (w), 874 (w), 818 (w), 768 (m),

756 (m), 739 (s), 723 (m), 712 (vs), 696 (s). Mp (°C) = >300.

16

4-Fluoro-4'-methoxy-1,1'-biphenyl (2a)

Using potassium tris(4-fluorophenyl)(4-methoxyphenyl)borate according to general

procedure G (0.40 mmol scale), provided 2a (0.33 mmol, 67 mg, 83%) as a white

solid. Rf = 0.21 (hexane/EtOAc 99:1, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 7.53 – 7.44 (m, 4H), 7.15 – 7.07 (m, 2H), 7.01 – 6.94 (m, 2H),

3.85 ppm (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 162.21 (d, J = 245.5 Hz),

159.2, 137.1, 132.9, 128.34 (d, J = 7.9 Hz), 128.2, 115.67 (d, J = 21.4 Hz), 114.4,

55.5 ppm. LRMS (EI pos): m/z (%): 202.1 (100), 187.1 (69), 159.1 (71), 133.1 (46), 107.1 (10).

Analytical data in accordance to literature.11

1,1'-Biphenyl (2b)

Using sodium tetraphenylborate according to general procedure G (0.40 mmol scale),

provided 2b (0.36 mmol, 56 mg, 91%) as a white solid. Rf = 0.9 (hexane/EtOAc 100:0,

UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.64 – 7.59 (m, 4H), 7.50 –

7.43 (m, 4H), 7.40 – 7.34 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 141.3, 128.9,

127.3, 127.1 ppm. LRMS (EI pos): m/z (%): 154.1 (100), 128.1 (9), 115.0 (10), 76.0

(26). Analytical data in accordance to literature.12

4-Methoxy-4'-(trifluoromethoxy)-1,1'-biphenyl (2c)

Using potassium trifluoro(4-methoxyphenyl)borate and (4-(trifluoromethoxy)phenyl)

magnesium bromide according to general procedure G (0.40 mmol scale), provided

2c (0.24 mmol, 64 mg, 60%) as a white solid. Rf = 0.35 (hexane/EtOAc 98:2, UV,

KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.56 – 7.50 (m, 2H), 7.50 – 7.44

(m, 2H), 7.24 (d, J = 7.3 Hz, 2H), 7.01 – 6.91 (m, 2H), 3.83 (s, 3H) ppm. 13C NMR

(101 MHz, Chloroform-d) δ 159.5, 148.3 (q, J = 1.9 Hz), 139.7, 132.5, 128.3, 128.1,

121.4, 120.7 (q, J = 256.9 Hz), 114.4, 55.5 ppm. LRMS (EI pos): m/z (%): 268.0

(100), 253.0 (37), 225.0 (42), 199.0 (16), 139.0 (13), 128.0 (21), 69.0 (18). Analytical data in

accordance to literature.13

11 W. Erb; M. Albini; J. Rouden; J. Blanchet, J. Org. Chem. 2014, 79, 10568−10580.

12 Y. Cheng, X. Gu, P. Li, Org. Lett. 2013, 15, 2664–2667. 13 I. R. Baxendale; C. M. Griffiths-Jones; S. V. Ley; G. K. Tranmer, Chem. Eur. J. 2006, 12, 4407-4416.

17

4-Methyl-4'-(trifluoromethoxy)-1,1'-biphenyl (2d)

Using potassium trifluoro(4-methylphenyl)borate and (4-

(trifluoromethoxy)phenyl)magnesium bromide according to general procedure G

(0.40 mmol scale), provided 2d (0.25 mmol, 64 mg, 63%) as a white solid. Rf = 0.6

(hexane, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.63 – 7.58 (m, 2H),

7.52 – 7.46 (m, 2H), 7.33 – 7.24 (m, 4H), 2.43 ppm (s, 3H). 13C NMR (101 MHz,

Chloroform-d) δ 148.56 (q, J = 1.8 Hz), 140.1, 137.7, 137.1, 129.8, 128.4, 127.1,

121.4, 120.69 (q, J = 257.0 Hz), 21.2 ppm. LRMS (EI pos): m/z (%): 252.1 (100), 237.0 (1),

183.1 (5), 167.1 (10). Analytical data in accordance to literature.14

Trimethyl(4'-(trifluoromethoxy)-[1,1'-biphenyl]-4-yl)silane (2e)

Using potassium trifluoro(4-(trimethylsilyl)phenyl)borate and (4-

(trifluoromethoxy)phenyl) magnesium bromide according to general procedure G

(0.40 mmol scale), provided 2e (0.26 mmol, 81 mg, 65%) as a white solid. Rf = 0.7

(hexane, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.66 – 7.60 (m, 4H),

7.59 – 7.55 (m, 2H), 7.36 – 7.27 (m, 2H), 0.33 ppm (s, 9H). 13C NMR (101 MHz,

Chloroform-d) δ 148.83 (q, J = 1.9 Hz), 148.8, 148.8, 148.8, 140.3, 140.03 (d, J = 5.3

Hz), 134.1, 128.6, 126.6, 121.5, 121.4, 120.68 (q, J = 257.1 Hz), -1.0. ppm. LRMS (EI

pos): m/z (%): 310.1 (10), 295.1 (100), 279.0 (2), 265.0 (2). HRMS (ESI-Quadrupole): m/z:

calcd for C16H17F3OSi+: 310.1001; found: 310.0998. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 2958

(w), 1715 (m), 1600 (vw), 1518 (w), 1492 (w), 1416 (w), 1361 (w), 1314 (w), 1250 (vs), 1218

(vs), 1207 (vs), 1161 (vs), 1116 (m). Mp (°C) = 50.

(3',5'-Bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)trimethylsilane (2f)

Using potassium trifluoro(4-(trimethylsilyl)phenyl)borate and (3,5-

bis(trifluoromethyl)phenyl) magnesium bromide according to general

procedure G (0.40 mmol scale), provided 2f (0.26 mmol, 94 mg, 65%) as a

white solid. Rf = 0.70 (hexane, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 8.02 (s, 2H), 7.87 (s, 1H), 7.67 (d, J = 8.1 Hz, 2H), 7.60 (d,

J = 8.1 Hz, 2H), 0.33 ppm (s, 9H). 13C NMR (101 MHz, Chloroform-

d) δ 143.5, 141.7, 138.6, 134.4, 132.24 (q, J = 33.2 Hz), 127.36 (d, J = 3.7 Hz), 126.6, 125.33

(q, J = 273.7, 272.6 Hz), 121.09 (p, J = 3.9 Hz), -1.0 ppm. LRMS (EI pos): m/z (%): 362.1 (15),

347.1 (100), 317.0 (5), 285.1 (5), 201.1 (5), 173.6 (5), 139.1 (5), 77.1 (5). HRMS (ESI-

Quadrupole): m/z: calcd for C17H16F6Si+: 362.0925; found: 362.0916. IR (Diamond-ATR,

neat) ��𝑚𝑎𝑥 (cm-1): 2959 (w), 2901 (w), 2013 (w), 1968 (w), 1917 (w), 1810 (w), 1620 (w), 1465

(w), 1381 (s), 1309 (w), 1276 (vs), 1263 (m), 1251 (s), 1171 (s), 1127 (vs), 1108 (s), 1052 (m),

14 J. Tang; A. Biafora; L. J. Goossen, Angew. Chem. Int. Ed. 2015, 44, 13130-13133.

18

1002 (w), 954 (w), 897 (m), 839 (s), 828 (s), 817 (vs), 759 (m), 724 (m), 704 (m), 678 (vs).

Mp (°C) = 44.

4'-Phenoxy-3,5-bis(trifluoromethyl)-1,1'-biphenyl (2g)

Using potassium trifluoro(4-phenoxyphenyl)borate and (3,5-

bis(trifluoromethyl)phenyl)magnesium bromide according to general

procedure G (0.40 mmol scale), provided 2g (0.33 mmol, 125 mg, 82%) as

a colorless oil. Rf = 0.30 (hexane, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 7.99 (s, 2H), 7.84 (s, 1H), 7.61 – 7.55 (m, 2H), 7.43 – 7.37

(m, 2H), 7.20 – 7.15 (m, 1H), 7.15 – 7.11 (m, 2H), 7.11 – 7.06 (m, 2H) ppm.

13C NMR (101 MHz, Chloroform-d) δ 158.5, 156.6, 142.8, 133.1, 132.2 (q, J = 33.2 Hz), 130.1,

128.8, 127.2 – 126.9 (m), 124.1, 123.5 (q, J = 272.7 Hz), 120.7 (p, J = 3.8 Hz), 119.5, 119.3

ppm. LRMS (EI pos): m/z (%): 382.1 (100), 354.1 (22), 277.0 (18), 237.0 (11), 219.0 (18),

215.1 (18), 188.0 (21), 182.0 (11), 141.1 (11), 77.0 (41). Analytical data in accordance to

literature.3

4-Phenoxy-4'-(trifluoromethoxy)-1,1'-biphenyl (2h)

Using potassium trifluoro(4-phenoxyphenyl)borate and (4-(trifluoromethoxy)phenyl)

magnesium bromide according to general procedure G (0.40 mmol scale), provided

2h (0.37 mmol, 122 mg, 92%) as a colourless oil. Rf = 0.10 (hexane, UV, KMnO4,

PAA). This reaction was also performed on a 3 mmol scale, giving 2h in 77% yield.1H

NMR (400 MHz, Chloroform-d) δ 7.60 – 7.55 (m, 2H), 7.54 – 7.50 (m, 2H), 7.40 –

7.34 (m, 2H), 7.30 – 7.26 (m, 2H), 7.16 – 7.12 (m, 1H), 7.10 – 7.05 ppm (m, 4H). 13C

NMR (101 MHz, Chloroform-d) δ 157.4, 157.0, 148.58 (d, J = 1.9 Hz), 139.5, 134.9,

130.0, 128.6, 128.3, 124.5, 123.7, 121.9, 121.4, 119.8, 119.3, 119.2, 116.8 ppm. LRMS (EI

pos): m/z (%): 330.1 (100), 315-1 (2), 301.1 (3), 261.1 (5). HRMS (ESI-Quadrupole): m/z:

calcd for C19H13F3O2+: 330.0868; found: 330.0862. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 3407

(w), 1710 (w), 1606 (w), 1597 (w), 1589 (m), 1490 (s), 1299 (s), 1268 (s), 1255 (s), 1220 (s),

1212 (s), 1163 (vs), 1154 (vs).

5-(3,5-Dimethylphenyl)benzo[d][1,3]dioxole (2i)

Using potassium benzo[d][1,3]dioxol-5-yltrifluoroborate and (3,5-

dimethylphenyl)magnesium bromide according to general procedure G

(0.40 mmol scale), provided 2i (0.21 mmol, 47 mg, 52%) as a white solid. Rf =

0.2 (hexane, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.15 (s, 2H),

7.09 – 7.04 (m, 2H), 6.99 – 6.97 (m, 1H), 6.87 (d, J = 7.9 Hz, 1H), 6.00 (s, 2H),

2.38 ppm (s, 6H). 13C NMR (101 MHz, Chloroform-d) δ 148.1, 147.0, 141.1, 138.4, 136.0,

128.7, 125.0, 120.7, 108.6, 107.9, 101.2, 21.5 ppm. LRMS (EI pos): m/z (%): 226.1 (100),

211.0 (2), 196.0 (3), 181.0 (5), 152.1 (30). HRMS (ESI-Quadrupole): m/z: calcd for C15H14O2+:

19

226.0994; found: 226.0992. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 3012 (vw), 2915 (w), 1715

(vw), 1600 (m), 1505 (m), 1489 (m), 1466 (s), 1422 (m), 1376 (w), 1336 (m), 1267 (w), 1234

(vs), 1204 (m), 1140 (w), 1109 (m), 1066 (w), 1037 (s). Mp (°C) = 60-64.

2-(4-Fluorophenyl)-6-methoxynaphthalene (2j)

Using potassium trifluoro(6-methoxynaphthalen-2-yl)borate and (4-

fluorophenyl)magnesium bromide according to general procedure G (0.40 mmol

scale), provided 2j (0.25 mmol, 64 mg, 63%) as a white solid. Rf = 0.23 (hexane,

UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.93 (d, J = 1.8 Hz, 1H),

7.80 (t, J = 7.9 Hz, 2H), 7.69 – 7.62 (m, 3H), 7.22 – 7.13 (m, 4H), 3.95 ppm (s, 3H).

13C NMR (101 MHz, Chloroform-d) δ 162.46 (d, J = 246.1 Hz), 157.9, 137.42 (d, J

= 3.3 Hz), 135.5, 133.8, 129.8, 129.2, 128.83 (d, J = 8.0 Hz), 127.5, 126.0, 125.6,

119.4, 115.78 (d, J = 21.4 Hz), 105.6, 55.4 ppm. LRMS (EI pos): m/z (%): 252.1

(100), 237.1 (15), 209.1 (80), 207.1 (30), 183.1 (15). Analytical data in accordance to

literature.15

4'-Fluoro-[1,1'-biphenyl]-3-ol (2k)

Using potassium trifluoro(3-hydroxyphenyl)borate and (4-

fluorophenyl)magnesium bromide (1.68 mmol, 4.2 equiv.) according to general

procedure G (0.40 mmol scale), provided 2k (0.35 mmol, 66 mg, 88%) as a white

solid. Rf = 0.23 (hexane/EtOAc 9:1, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 7.56 – 7.49 (m, 2H), 7.30 (t, J = 7.9 Hz, 1H), 7.15 – 7.08 (m, 3H),

7.01 (t, 1H), 6.82 (ddd, J = 8.1, 2.6, 0.9 Hz, 1H), 4.90 ppm (s, 1H). 13C

NMR (101 MHz, Chloroform-d) δ 162.68 (d, J = 246.5 Hz), 156.0, 142.2, 136.95 (d, J =

3.3 Hz), 130.2, 128.8, 128.8, 119.8, 115.76 (d, J = 21.4 Hz), 114.20 ppm (d, J = 19.1 Hz).

LRMS (EI pos): m/z (%): 188.0 (100), 159.0 (30), 133.0 (25), 120.0 (10), 94.0 (10). Analytical

data in accordance to literature.16

4'-(Trifluoromethoxy)-[1,1'-biphenyl]-3-ol (2l)

Using potassium trifluoro(3-hydroxyphenyl)borate and (4-

(trifluoromethoxy)phenyl)magnesium bromide (1.68 mmol, 4.2 equiv.) according

to general procedure G (0.40 mmol scale), provided 2l (0.19 mmol, 49 mg, 48%)

as a white solid. Rf = 0.60 (hexane/EtOAc 7:3, UV, KMnO4, PAA). 1H NMR

(400 MHz, Chloroform-d) δ 7.53 (dt, J = 8.8, 2.8, 2.1 Hz, 2H), 7.28 (t, J = 7.9 Hz,

1H), 7.24 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 7.7 Hz, 1H), 6.99 (t, J = 2.1 Hz, 1H),

6.80 (ddd, J = 8.1, 2.6, 0.9 Hz, 1H), 4.85 ppm (s, 1H). 13C NMR (101 MHz, Chloroform-

15 S. E. Denmark; R. C. Smith; W.-T. T. Chang; J. M. Muhuh, J. Am. Chem. Soc. 2009, 131, 3104–3118. 16 J. Luo; S. Preciado; S. O. Araromi; I. Larrosa, Chem. - Asian J. 2016, 11, 347–350.

20

d) δ 155.9, 148.8, 141.6, 139.5, 130.2, 128.5, 121.2, 120.5 (d, J = 257.2 Hz), 119.7, 114.6,

114.1 ppm. LRMS (EI pos): m/z (%): 254.1 (100), 225.1 (10), 185.1 (20), 157.1 (30), 139.1

(10), 128.1 (20), 69.0 (15). Analytical data in accordance to literature.17

N,N-Diisopropyl-4'-phenoxy-[1,1'-biphenyl]-4-carboxamide (2m)

Using potassium trifluoro(4-phenoxyphenyl)borate and (4-

(diisopropylcarbamoyl)phenyl)zinc iodide according to general procedure G

(0.40 mmol scale), provided 2m (0.21 mmol, 79 mg, 53%) as a colourless oil.

Rf = 0.4 (hexane/EtOAc 80:20, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 7.60 – 7.52 (m, 4H), 7.42 – 7.34 (m, 4H), 7.16 – 7.11 (m, 1H),

7.10 – 7.04 (m, 4H), 4.08 – 3.43 (m, 2H), 1.65 – 1.18 ppm (m, 12H). 13C

NMR (101 MHz, Chloroform-d) δ 171.0, 157.2, 157.1, 141.0, 137.6, 135.5,

129.9, 128.5, 127.0, 126.3, 123.6, 119.2, 119.1, 50.9, 48.0, 20.9 ppm. LRMS (EI pos): m/z (%):

373.2 (5), 330.2 (20), 273.1 (100). HRMS (ESI-Quadrupole): m/z: calcd for C25H27NO2+:

373.2042; found: 373.2036. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 2968 (w), 2931 (w), 1627 (s),

1588 (m), 1521 (m), 1488 (s), 1438 (m), 1377 (m), 1370 (m), 1359 (w), 1338 (s), 1238 (vs),

1213 (m), 1194 (w), 1167 (m), 1136 (w).

4'-Phenoxy-[1,1'-biphenyl]-4-carbonitrile (2n)

Using potassium trifluoro(4-phenoxyphenyl)borate and (4-cyanophenyl)zinc iodide

according to general procedure G (0.50 mmol scale), provided 2n (0.19 mmol, 51 mg,

47%) as a colorless oil. Rf = 0.14 (hexane/EtOAc 98:2, UV, KMnO4, PAA). 1H NMR

(400 MHz, Chloroform-d) δ 7.74 – 7.69 (m, 2H), 7.68 – 7.63 (m, 2H), 7.58 – 7.52 (m,

2H), 7.41 – 7.35 (m, 2H), 7.16 (ddt, J = 8.5, 7.2, 1.1 Hz, 1H), 7.12 – 7.05 (m, 4H) ppm.

13C NMR (101 MHz, Chloroform-d) δ 158.4, 156.6, 145.1, 134.0, 132.8, 130.1, 128.8,

127.5, 124.0, 119.6, 119.1, 119.1, 110.7 ppm. LRMS (EI pos): m/z (%): 271.1 (100), 242.1 (12),

207.0 (86), 190.9 (12), 166.1 (17), 140.1 (19), 77.0 (36). Analytical data in accordance to

literature.18

5-(3,5-Bis(trifluoromethyl)phenyl)benzo[c][1,2,5]oxadiazole (2o)

Using potassium benzo[c][1,2,5]oxadiazol-5-yltrifluoroborate and (3,5-


procedure G (0.40 mmol scale), provided 2o (0.27 mmol, 88 mg, 68%) as a

white solid. Rf = 0.48 (hexane/EtOAc 98:2, UV, KMnO4, PAA). 1H NMR (400

MHz, Chloroform-d) δ 8.09 (s, 2H), 8.08 – 8.06 (m, 1H), 8.03 (dd, J = 9.3,

0.9 Hz, 1H), 7.99 (s, 1H), 7.70 (dd, J = 9.3, 1.5 Hz, 1H) ppm. 13C NMR (101

MHz, Chloroform-d) 149.5, 148.7, 141.5, 141.1, 132.9 (q, J = 33.7 Hz), 131.8, 127.6, 123.2 (q,

17 J. J. Molloy; R. P. Law; J. W. B. Fyfe; C. P. Seath; D. J. Hirst; A. J. B. Watson; Org. Biomol. Chem. 2015, 13, 3093–3102. 18 S. Yang; C. Wu; H. Zhou; Y. Yang; Y. Zhao; C. Wang; W. Yang; J. Xu, Adv. Synth. Catal. 2013, 355, 53−58.

21

J = 272.9 Hz), 122.9 (p, J = 3.7 Hz), 118.1, 114.9 ppm. LRMS (EI pos): m/z (%): 332.0 (100),

312.0 (34), 302.0 (22), 282.0 (61), 265.0 (24), 237.0 (16), 213.0 (30), 164.0 (13). Analytical

data in accordance to literature.3

5-(4-(Trifluoromethoxy)phenyl)benzo[c][1,2,5]oxadiazole (2p)

Using potassium benzo[c][1,2,5]oxadiazol-5-yltrifluoroborate and (4-


(0.40 mmol scale), provided 2p (0.28 mmol, 78 mg, 70%) as a yellow oil. Rf = 0.55

(hexane/EtOAc 9:1, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.96 –

7.91 (m, 2H), 7.71 – 7.64 (m, 3H), 7.37 ppm (d, J = 8.0 Hz, 2H). 13C NMR (101 MHz,

Chloroform-d) δ 150.0, 149.7, 148.7, 143.0, 137.5, 132.6, 129.0, 121.7, 120.19 (q,

J = 257.8 Hz), 117.2, 113.3 ppm. LRMS (EI pos): m/z (%): 280.0 (100), 263.0 (10),

250.0 (70), 223.0 (25), 195.0 (15), 177.0 (10), 165.0 (15), 153.0 (30), 126.0 (25), 69.0 (35).

HRMS (ESI-Quadrupole): m/z: calcd for C13H7F3N2O2+: 280.0460; found: 280.0450.

IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 2389 (vw), 2054 (vw), 1979 (vw), 1940 (vw), 1908 (w),

1781 (w), 1723 (vw), 1690 (vw), 1630 (w), 1608 (w), 1590 (w), 1543 (vw), 1520 (m), 1505 (w),

1467 (w), 1405 (w), 1374 (w), 1308 (w), 1251 (s), 1206 (vs), 1153 (vs), 1110 (m), 1021 (m),

993 (m), 922 (m), 881 (m), 850 (m), 802 (vs), 782 (s), 762 (w), 739 (m), 714 (w), 674 (m).

5-(4-Fluorophenyl)benzo[c][1,2,5]oxadiazole (2q)

Using potassium benzo[c][1,2,5]oxadiazol-5-yltrifluoroborate and (4-


scale), provided 2q (0.24 mmol, 51 mg, 59%) as a light-yellow solid. Rf = 0.44

(hexane/EtOAc 9:1, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 7.93 –

7.88 (m, 2H), 7.67 (dd, J = 9.1, 1.7 Hz, 1H), 7.65 – 7.60 (m, 2H), 7.24 – 7.17 ppm

(m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 163.49 (d, J = 249.6 Hz), 149.8,

148.6, 143.4, 135.0, 132.8, 129.25 (d, J = 8.4 Hz), 117.0, 116.40 (d, J = 21.7 Hz),

112.69 ppm (d, J = 1.2 Hz). LRMS (EI pos): m/z (%): 214.0 (100), 197.0 (10), 184.0 (90), 158.0

(60), 157.0 (70), 133.0 (20), 120.0 (20), 107.0 (20), 75.0 (20), 57.0 (15). HRMS (ESI-

Quadrupole): m/z: calcd for C12H7FN2O+: 214.0542; found: 214.0532. IR (Diamond-ATR,

neat) ��𝑚𝑎𝑥 (cm-1): 2961 (w), 1964 (w), 1600 (m), 1519 (m), 1502 (m), 1466 (m), 1418 (w), 1403

(w), 1379 (w), 1373 (w), 1319 (w), 1302 (w), 1261 (w), 1223 (m), 1165 (m), 1101 (m), 1042

(w), 1018 (m), 994 (m), 959 (w), 880 (m), 870 (w), 839 (m), 814 (m), 801 (vs), 779 (m), 761

(w), 738 (w), 718 (w), 696 (m), 680 (w), 674 (w), 668 (w). Mp (°C) = 112.

22

2-(4-Fluorophenyl)benzofuran (2r)

Using potassium benzofuran-2-yltrifluoroborate and (4-fluorophenyl)magnesium

bromide according to general procedure G (0.40 mmol scale), provided 2r

(0.28 mmol, 59 mg, 69%) as a white solid. Rf = 0.7 (hexane, UV, KMnO4, PAA). 1H

NMR (400 MHz, Chloroform-d) δ 7.89 – 7.82 (m, 2H), 7.60 (d, J = 7.3 Hz, 1H), 7.53

(d, J = 7.6 Hz, 1H), 7.30 (td, J = 8.1, 7.7, 1.5 Hz, 1H), 7.27 – 7.22 (m, 1H), 7.21 – 7.11

(m, 2H), 6.97 ppm (s, 1H). 13C NMR (101 MHz, Chloroform-d) δ 163.00 (d, J =

248.7 Hz), 155.1, 155.0, 129.3, 126.90 (d, J = 8.2 Hz), 126.9, 124.4, 123.2, 121.0, 116.03 (d,

J = 22.0 Hz), 111.3, 101.13 ppm (d, J = 1.8 Hz). LRMS (EI pos): m/z (%): 212.1 (100), 183.1

(55), 157.0 (10). Analytical data in accordance to literature.19

5-(3,5-Bis(trifluoromethyl)phenyl)-2-methoxypyridine (2s)

Using potassium trifluoro(6-methoxypyridin-3-yl)borate and 3,5-


procedure G (0.40 mmol scale), provided 2s (0.14 mmol, 45 mg, 35%) as a

colorless oil. Rf = 0.46 (hexane/EtOAc 95:5, UV, KMnO4, PAA). 1H NMR

(400 MHz, Chloroform-d) δ 8.41 (dd, J = 2.6, 0.8 Hz, 1H), 7.94 (s, 2H), 7.85

(s, 1H), 7.81 (dd, J = 8.6, 2.6 Hz, 1H), 6.87 (dd, J = 8.7, 0.8 Hz, 1H), 4.00

(s, 3H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 164.7, 145.6, 140.3, 137.4, 132.5 (q, J =

33.3 Hz), 127.4, 126.8, 123.4 (q, J = 272.8 Hz), 121.1 (p, J = 3.8 Hz), 111.6, 53.9 ppm. LRMS

(EI pos): m/z (%): 320.1 (100), 302.1 (14), 292.1 (47), 270.0 (24), 222.1 (12), 202.0 (14), 182.1


6-(4-Fluorophenyl)-2-methylquinoline (2t)

Using potassium trifluoro(2-methylquinolin-6-yl)borate and (4-


scale), provided 2t (0.22 mmol, 53 mg, 56%) as a white solid. Rf = 0.15 (hexane,

UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-d) δ 8.08 (d, J = 8.1 Hz, 2H),

7.91 – 7.86 (m, 2H), 7.69 – 7.62 (m, 2H), 7.31 (d, J = 8.4 Hz, 1H), 7.21 – 7.13 (m,

2H), 2.76 ppm (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 162.75 (d, J =

247.0 Hz), 159.3, 147.2, 137.6, 136.70 (d, J = 3.3 Hz), 136.5, 129.2, 129.08 (d, J =

8.0 Hz), 129.0, 126.8, 125.2, 122.7, 115.96 (d, J = 21.4 Hz), 25.5 ppm. LRMS (EI

pos): m/z (%): 237.1 (100), 236.0 (15), 221.1 (10), 209.1 (10), 194.1 (10), 183 (10), 118.5 (10).

HRMS (ESI-Quadrupole): m/z: calcd for C16H12FN+: 237.0954; found: 237.0945. IR (Diamond-

ATR, neat) ��𝑚𝑎𝑥 cm-1 (cm-1): 1601 (m), 1592 (w), 1516 (m), 1491 (m), 1466 (w), 1414 (w), 1389

(w), 1371 (w), 1341 (w), 1314 (w), 1301 (w), 1224 (m), 1161 (m), 1125 (w), 1100 (w), 1029 (w),

19 X. Wang; M. Liu; L. Xu, Q. Wang; J. Chen; J. Ding; H. Wu, J. Org. Chem. 2013, 78, 5273-5281.

23

1013 (w), 976 (w), 965 (w), 951 (w), 893 (m), 849 (w), 828 (vs), 820 (s), 799 (w), 776 (w), 761

(w), 750 (w), 733 (w), 718 (w), 697 (w), 668 (w), 659 (w). Mp (°C) = 94.

2-(p-Tolyl)dibenzo[b,d]furan (2u)

Using potassium trifluoro(p-tolyl)borate and dibenzo[b,d]furan-2-yl-magnesium

bromide according to general procedure G (0.40 mmol scale), provided 2u

(0.31 mmol, 81 mg, 78%) as a light yellow solid. Rf = 0.44 (hexane, UV, KMnO4,

PAA). 1H NMR (400 MHz, Chloroform-d) δ 8.13 (d, J = 1.4 Hz, 1H), 8.00 (ddd,

J = 7.6, 1.4, 0.7 Hz, 1H), 7.67 (dd, J = 8.5, 1.9 Hz, 1H), 7.63 – 7.55 (m, 4H),

7.48 (td, J = 8.3, 7.8, 1.3 Hz, 1H), 7.36 (td, J = 7.5, 1.0 Hz, 1H), 7.29 (d, J =

7.8 Hz, 2H), 2.43 ppm (s, 3H). 13C NMR (101 MHz, Chloroform-d) δ 156.8,

155.7, 138.6, 137.0, 136.5, 129.7, 127.4, 126.6, 124.8, 124.4, 122.9, 120.8, 119.1, 111.9,

111.9, 21.3 ppm. LRMS (EI pos): m/z (%): 258.0 (100), 242.2 (10), 228.2 (10), 213.2 (10),

202.2 (10), 129.1 (10). HRMS (ESI-Quadrupole): m/z: calcd for C19H14O+: 258.1045; found:

258.1039. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 3023 (w), 2918 (w), 2860 (w), 1936 (vw), 1896

(vw), 1602 (w), 1589 (w), 1519 (vw), 1473 (s), 1446 (s), 1431 (m), 1407 (w), 1377 (w), 1340

(w), 1320 (w), 1295 (w), 1285 (w), 1274 (w), 1253 (m), 1242 (w), 1193 (s), 1149 (w), 1122 (m),

1105 (m), 1022 (m), 1012 (w), 932 (w), 884 (w), 869 (w), 841 (m), 829 (m), 801 (vs), 766 (m),

745 (vs), 729 (s), 717 (m), 698 (m), 674 (m), 662 (m). Mp (°C) = 86.

1-(3',5'-Bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)-5-(p-tolyl)-3-(trifluoromethyl)-1H -

pyrazole (2v)

Using potassium trifluoro(4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-

1-yl)phenyl)borate and (3,5-bis(trifluoromethyl)phenyl)magnesium

bromide according to general procedure G (0.40 mmol scale),

provided 2v (0.15 mmol, 78 mg, 38%) as a colorless oil. Rf = 0.35

(hexane/EtOAc 98:2, UV, KMnO4, PAA). 1H NMR (400 MHz,

Chloroform-d) δ 8.01 (s, 2H), 7.89 (s, 1H), 7.66 – 7.59 (m, 2H), 7.51 –

7.45 (m, 2H), 7.17 (d, J = 1.7 Hz, 4H), 6.76 (s, 1H), 2.38 ppm (s, 3H).

13C NMR (101 MHz, Chloroform-d) δ 145.1, 143.72 (q, J = 38.4 Hz),

142.0, 139.9, 139.6, 138.0, 132.44 (q, J = 33.4 Hz), 129.6, 128.8, 127.9, 127.31 (d, J = 4.1 Hz),

126.3, 126.1, 123.39 (q, J = 272.8 Hz), 121.55 (p, J = 3.9 Hz), 121.38 (q, J = 269.0 Hz), 105.98

(q, J = 2.0 Hz), 21.5 ppm. LRMS (EI pos): m/z (%): 514.2 (100), 493.2 (15), 445.2 (10), 301.1


24

4-Iodo-4'-(trifluoromethoxy)-1,1'-biphenyl (2w)

Using potassium trifluoro(4-iodophenyl)borate and (4-


(0.40 mmol scale), provided 2w (0.25 mmol, 89 mg, 61%) as a colourless oil. Rf =

0.7 (hexane, UV, KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 7.83 – 7.72 (m, 2H),

7.61 – 7.51 (m, 2H), 7.32 – 7.27 ppm (m, 4H). 13C NMR (101 MHz, Chloroform-

d) δ 149.0, 139.5, 138.9, 138.1, 129.1, 128.4, 121.5, 120.6 (q, J = 257.3 Hz),

93.7 ppm. LRMS (EI pos): m/z (%): 364.1 (100), 295.0 (10), 267.0 (10). HRMS (ESI-

Quadrupole): m/z: calcd for C13H8F3IO+: 363.9572; found: 363.9572. IR (Diamond-ATR,

neat) ��𝑚𝑎𝑥 (cm-1): 1606 (w), 1587 (w), 1582 (w), 1520 (w), 1478 (m), 1387 (w), 1328 (w), 1307

(m), 1255 (s), 1205 (s), 1161 (vs), 1109 (w), 1070 (m), 999 (m), 929 (w), 852 (w), 808 (s), 766

(w), 748 (w).

4-Bromo-4'-(trifluoromethoxy)-1,1'-biphenyl (2x)

Using potassium trifluoro(4-bromophenyl)borate and (4-


(0.40 mmol scale), provided 2x (0.28 mmol, 88 mg, 69%) as colourless oil. Rf = 0.7

(hexane, UV, KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 7.60 – 7.53 (m, 4H), 7.46

– 7.39 (m, 2H), 7.34 – 7.27 ppm (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 149.0,

138.9, 132.2, 128.8, 128.6, 128.4, 122.2, 121.5, 120.62 ppm (q, J = 257.3 Hz).

LRMS (EI pos): m/z (%): 316.0 (100), 247.0 (20), 219.0 (25). Analytical data in

accordance to literature.20

4-Chloro-4'-iodo-3-(trifluoromethyl)-1,1'-biphenyl (2y)

Using potassium trifluoro(4-iodophenyl)borate and (4-chloro-3-

(trifluoromethyl)phenyl) magnesium according to general procedure G

(0.40 mmol scale), provided 2y (0.26 mmol, 101 mg, 66%) as a light yellow oil.

Rf = 0.5 (hexane, UV, KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 7.85 (d, J =

2.2 Hz, 1H), 7.82 – 7.77 (m, 2H), 7.64 (dd, J = 8.4, 2.2 Hz, 1H), 7.57 (d, J = 8.4

Hz, 1H), 7.32 – 7.27 ppm (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 139.1,

138.4, 138.2, 132.1, 131.77 (q, J = 1.9 Hz), 131.1, 129.41 – 129.10 (m), 128.9, 127.0, 126.01

(q, J = 5.4 Hz), 122.88 (q, J = 273.4 Hz), 94.5 ppm. LRMS (EI pos): m/z (%): 382.1 (100),

363.0 (5), 220.1 (60). HRMS (ESI-Quadrupole): m/z: calcd for C13H7ClF3I+: 381.9233; found:

381.9237. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 1474 (m), 1417 (m), 1384 (w), 1327 (s),

1282 (w), 1268 (m), 1260 (m), 1253 (m), 1193 (w), 1170 (m), 1137 (s), 1126 (vs), 1116 (vs),

20 Y. Ding; L. Mao; D. Xu; H. Xie; L. Yang; H. Xu; W. Geng; Y. Gao; C. Xia; X. Zhang; Q. Meng; D. Wu; J. Zhao, Bioorg. Med. Chem. Lett. 2015, 25, 2744.

25

1065 (w), 1035 (m), 1030 (m), 1003 (m), 905 (m), 835 (w), 811 (vs), 763 (w), 740 (w), 688 (w),

665 (m).

2-(4-Iodophenyl)dibenzo[b,d]furan (2z)

Using potassium trifluoro(4-iodophenyl)borate and dibenzo[b,d]furan-2-yl-

magnesium bromide according to general procedure G (0.40 mmol scale),

provided 2z (0.24 mmol, 90 mg, 61%) as a colourless oil. Rf = 0.3 (hexane, UV,

KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 8.10 (s, 1H), 7.99 (d, J = 7.6 Hz,

1H), 7.85 – 7.75 (m, 2H), 7.66 – 7.55 (m, 3H), 7.49 (ddd, J = 8.3, 7.2, 1.4 Hz,

1H), 7.44 – 7.34 ppm (m, 3H). 13C NMR (101 MHz, Chloroform-d) δ 156.8,

156.0, 141.0, 138.0, 135.3, 129.4, 127.6, 126.4, 125.0, 124.2, 123.0, 120.9,

119.1, 112.1, 112.0, 92.9 ppm. LRMS (EI pos): m/z (%): 370.1 (100), 242.2 (30), 213.1 (30).

HRMS (ESI-Quadrupole): m/z: calcd for C18H11OI+: 369.9855; found: 369.9846. IR (Diamond-

ATR, neat) ��𝑚𝑎𝑥 (cm-1): 3053 (w), 1468 (vs), 1447 (s), 1391 (w), 1339 (w), 1318 (w), 1306 (w),

1284 (w), 1262 (w), 1250 (w), 1200 (s), 1185 (m), 1124 (w), 1104 (w), 1063 (w), 1022 (w),

1000 (m), 841 (m), 804 (s), 780 (m), 766 (w), 747 (s), 724 (m).

4'-Fluoro-[1,1'-biphenyl]-4-carbonitrile (2aa)

Using potassium (4-cyanophenyl)trifluoroborate and (4-fluorophenyl)magnesium

bromide according to general procedure G (0.40 mmol scale), provided 2aa

(0.19 mmol, 38 mg, 47%) as a colourless oil. Rf = 0.15 (hexane/EtOAc 98:2, UV,

KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 7.75 – 7.69 (m, 2H), 7.66 – 7.61 (m, 2H),

7.59 – 7.52 (m, 2H), 7.21 – 7.13 ppm (m, 2H). 13C NMR (101 MHz, Chloroform-

d) δ 163.3 (d, J = 248.9 Hz), 144.7, 135.4 (d, J = 3.3 Hz), 132.8, 129.1 (d, J = 8.2 Hz),

127.7, 119.0, 116.3 (d, J = 21.8 Hz), 111.1 ppm. LRMS (EI pos): m/z (%): 197.1 (100), 169.1

(10), 75.0 (9). Analytical data in accordance to literature.21

4'-(Trifluoromethoxy)-[1,1'-biphenyl]-4-carbonitrile (2ab)

Using potassium (4-cyanophenyl)trifluoroborate and (4-


(0.40 mmol scale), provided 2ab (0.25 mmol, 66 mg, 63%) as a colourless oil. Rf =

0.3 (hexane/EtOAc 96:4, UV, KMnO4). 1H NMR (400 MHz, Chloroform-d) δ 7.76 –

7.72 (m, 2H), 7.69 – 7.64 (m, 2H), 7.63 – 7.58 (m, 2H), 7.33 ppm (d, J = 8.0 Hz, 2H).

13C NMR (101 MHz, Chloroform-d) δ 149.7, 144.3, 138.0, 132.9, 128.8, 127.8,

121.6, 120.56 (q, J = 257.7 Hz), 118.9, 111.5 ppm. LRMS (EI pos): m/z (%): 263.1

(100), 194.1 (40), 178.1 (5), 166.1 (50). Analytical data in accordance to literature.22

21 Y. Gan, G. Wang, X. Xie, Y. Liu J. Org. Chem. 2018, 83, 14036–14048. 22 M. S. Hofmayer; F. H. Lutter; L. Grokenberger; J. M. Hammann; P. Knochel, Org. Lett. 2019, 21, 36.

26

(E)-1-Fluoro-4-styrylbenzene (4a)

Using potassium (E)-trifluoro(styryl)borate and (4-fluorophenyl)magnesium bromide

according to general procedure H (0.4 mmol scale), provided 4a (0.23 mmol, 45 mg,

57%, E/Z = 99:1) as colourless solid. Rf = 0.7 (hexane, UV, KMnO4, PAA). 1H NMR

(400 MHz, CDCl3) δ 7.46-7.35 (m, 4H), 7.27 (t, J = 7.7 Hz, 2H), 7.21-7.13 (m, 1H),

7.03-6.92 ppm (m, 4H). 13C NMR (101 MHz, CDCl3) δ 162.34 (d, J = 247.2 Hz),

137.2, 133.51 (d, J = 3.3 Hz), 128.7, 128.49 (d, J = 2.5 Hz), 128.01 (d, J = 8.0 Hz),

127.7, 127.5, 126.5, 115.65 ppm (d, J = 21.6 Hz). LRMS (DEP/EI-Orbitrap): m/z

(%): 198.0 (100), 183.0 (45), 177.0 (20). Analytical data in accordance to literature.23

(E)-4-(4-Fluorostyryl)-1,1'-biphenyl (4b)

Using potassium (E)-(2-([1,1'-biphenyl]-4-yl)vinyl)trifluoroborate and (4-

fluorophenyl)magnesium bromide according to general procedure H (0.4 mmol

scale), provided 4b (0.23 mmol, 63 mg, 57%, E/Z = 99:1) as colourless solid. 1H

NMR (400 MHz, CDCl3) δ 7.69-7.55 (m, 6H), 7.55-7.42 (m, 4H), 7.40-7.31 (m, 1H),

7.15-7.00 ppm (m, 4H). 13C NMR (101 MHz, CDCl3) δ 162.35 (d, J = 247.2 Hz),

140.6, 140.4, 136.2, 133.50 (d, J = 3.3 Hz), 128.8, 128.1, 128.0, 127.5, 127.4, 126.9,

126.9, 115.67 ppm (d, J = 21.6 Hz). LRMS (DEP/EI-Orbitrap): m/z (%): 274.1 (100),

259.0 (10), 252.1 (15). Analytical data in accordance to literature.24

(E)-1-Styrylnaphthalene (4c)

Using potassium (E)-trifluoro(styryl)borate and naphthalen-1-ylmagnesium

bromide according to general procedure H (0.4 mmol scale), provided 4c

(0.30 mmol, 68 mg, 74%, E/Z = 99:1) as colourless solid. 1H NMR (400 MHz,

CDCl3) δ 8.23 (d, J = 8.0 Hz, 1H), 7.93-7.86 (m, 2H), 7.82 (d, J = 8.2 Hz, 1H),

7.76 (d, J = 6.1 Hz, 1H), 7.65-7.60 (m, 2H), 7.58-7.48 (m, 3H), 7.42 (t, J = 7.7 Hz,

2H), 7.34-7.29 (m, 1H), 7.17 ppm (d, J = 16.0 Hz, 1H). 13C NMR (101 MHz, CDCl3)

δ 137.7, 135.1, 133.8, 131.9, 131.5, 128.9, 128.8, 128.2, 127.9, 126.8, 126.2, 126.0, 125.9,

125.8, 123.9, 123.8 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 229.1 (100), 215.1 (15), 202.1


23 A. L. Isfahani; I. Mohammadpoor-Baltork; V. Mirkhani; A. R. Khosropour; M. Moghadam; S. Tangestaninejad; R. Kia, Adv. Synth. Catal. 2013, 355, 957-972. 24 Y. Liu; P. Liu; Y. Wei, Chin. J. Chem. 2017, 35, 1141. 25 M. Das; D. F. O´Shea, Org. Lett. 2016, 18, 336.

27

(E)-1,2-Diphenylethene (4d)

Using potassium (E)-trifluoro(styryl)borate and phenylmagnesium bromide

according to general procedure H (0.4 mmol scale), provided 4d (0.22 mmol, 40 mg,

56%, E/Z = 99:1) as colourless solid. Rf = 0.6 (hexane, UV, KMnO4, PAA). 1H NMR

(400 MHz, CDCl3) δ 7.47 – 7.41 (m, 4H), 7.28 (t, J = 7.6 Hz, 4H), 7.23 – 7.14 (m,

2H), 7.04 ppm (s, 2H). 13C NMR (101 MHz, CDCl3) δ 137.3, 128.7, 127.6,

126.5 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 180.1 (100), 165.1 (50), 152.1 (30),

139.1 (10). Analytical data in accordance to literature.26

(E)-1-Chloro-3-styrylbenzene (4e)

Using potassium (E)-trifluoro(styryl)borate and (3-chlorophenyl)magnesium

bromide according to general procedure H (0.4 mmol scale), provided 4e

(0.19 mmol, 40 mg, 47%, E/Z = 99:1) as colourless oil. Rf = 0.6 (hexane, UV,

KMnO4, PAA). 1H NMR (400 MHz, CDCl3) δ 7.56 – 7.46 (m, 3H), 7.43 – 7.34 (m,

3H), 7.33 – 7.20 (m, 3H), 7.12 (d, J = 16.3 Hz, 1H), 7.04 ppm (d, J = 16.3 Hz, 1H).

13C NMR (101 MHz, CDCl3) δ 139.4, 136.9, 134.8, 130.2, 130.0, 128.9, 128.2,

127.6, 127.3, 126.8, 126.4, 124.9 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 214.1 (50), 199.0


4'-Fluoro-2,3,4,5-tetrahydro-1,1'-biphenyl (4f)

Using potassium cyclohex-1-en-1-yltrifluoroborate and (4-fluorophenyl)magnesium

bromide according to general procedure H (0.4 mmol scale), provided 4f (0.17 mmol,

30 mg, 43%) as colourless oil. 1H NMR (400 MHz, CDCl3) δ 7.41-7.29 (m, 2H), 7.03-

6.92 (m, 2H), 6.06 (tt, J = 3.9, 1.8 Hz, 1H), 2.37 (ddq, J = 6.3, 4.3, 2.2 Hz, 2H), 2.20

(dtt, J = 8.8, 6.1, 2.6 Hz, 2H), 1.85-1.74 (m, 2H), 1.70-1.60 ppm (m, 2H). 13C NMR

(101 MHz, CDCl3) δ 161.75 (d, J = 244.9 Hz), 138.8, 135.6, 126.37 (d, J = 7.7 Hz), 124.7,

114.88 (d, J = 21.2 Hz).,27.5, 25.8, 23.0, 22.1 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 176.1


4-Phenyl-3,6-dihydro-2H-pyran (4g)

Using potassium (3,6-dihydro-2H-pyran-4-yl)trifluoroborate and phenylmagnesium

bromide according to general procedure H (0.4 mmol scale), provided 4g (0.16 mmol,

25 mg, 39%) as colourless oil. 1H NMR (400 MHz, CDCl3) δ 7.42-7.38 (m, 2H), 7.37-

7.32 (m, 2H), 7.30-7.24 (m, 1H), 6.13 (tt, J = 3.0, 1.6 Hz, 1H), 4.33 (q, J = 2.8 Hz, 2H),

3.94 (t, J = 5.5 Hz, 2H), 2.74-2.34 ppm (m, 2H). 13C NMR (101 MHz, CDCl3) δ 140.4,

26 A. Modak; A. Deb; T. Petra; S. Rana; S. Maity; D. Maiti, Chem. Commun. 2012, 48, 4253. 27 S. Fu; N.-Y. Chen; X. Liu; Z. Shao; S.-P. Luo; Q. Liu, J. Am. Chem. Soc. 2016, 138, 8588. 28 K. Ishizuka; H. Seike; T. Hatakeyama; M. Nakamura, J. Am. Chem. Soc. 2010, 132, 13117.

28

134.2, 128.6, 127.4, 124.8, 122.6, 66.0, 64.6, 27.3 ppm. LRMS (DEP/EI-Orbitrap): m/z (%):

160.1 (100), 145.1 (10), 131.1 (100). Analytical data in accordance to literature.29

4-(3,5-Bis(trifluoromethyl)phenyl)-3,6-dihydro-2H-pyran (4h)

Using potassium (3,6-dihydro-2H-pyran-4-yl)trifluoroborate and (3,5-

bis(trifluoromethyl)phenyl) magnesium bromide according to general

procedure H (0.4 mmol scale), provided 4h (0.11 mmol, 33 mg, 28%) as

colourless oil. Rf = 0.3 (hexane/EtOAc 9:1, UV, PAA, KMnO4). 1H NMR

(400 MHz, CDCl3) δ 7.80 (s, 2H), 7.76 (s, 1H), 6.31 (tt, J = 3.0, 1.6 Hz, 1H),

4.36 (q, J = 2.9 Hz, 2H), 3.96 (t, J = 5.4 Hz, 2H), 2.59-2.51 ppm (m, 2H). 13C NMR (101 MHz,

CDCl3) δ 142.3, 132.3, 131.89 (q, J = 33.1 Hz), 126.3, 125.05-124.76 (m), 123.51 (d, J = 271.9

Hz), 121.09-120.83 (m), 65.8, 64.2, 27.1 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 296.1 (100),

278.1 (70), 267.1 (80), 254.1 (20).6

4-(3,5-Dimethylphenyl)-3,6-dihydro-2H-pyran (4i)

Using potassium (3,6-dihydro-2H-pyran-4-yl)trifluoroborate and (3,5-

dimethylphenyl)magnesium bromide according to general procedure H (0.4 mmol

scale), provided 4i (0.28 mmol, 52 mg, 69%) as colourless oil. Rf = 0.35

(hexane/EtOAc 98:2, UV, KMnO4). 1H NMR (400 MHz, CDCl3) δ 7.02 (s, 2H), 6.92

(s, 1H), 6.09 (tt, J = 3.1, 1.6 Hz, 1H), 4.32 (q, J = 2.8 Hz, 2H), 3.93 (t, J = 5.5 Hz,

2H), 2.54-2.48 (m, 2H), 2.33 ppm (s, 6H). 13C NMR (101 MHz, CDCl3) δ 140.5, 138.0, 134.4,

129.1, 122.8, 122.2, 66.0, 64.7, 27.5, 21.5 ppm. LRMS (DEP/EI-Orbitrap): m/z (%): 188.1

(100), 173.1 (90), 159.1 (35), 145.1 (100).6

8-(4-(Trifluoromethoxy)phenyl)-1,4-dioxaspiro[4.5]dec-7-ene (4j)

Using potassium trifluoro(1,4-dioxaspiro[4.5]dec-7-en-8-yl)borate and (4-

(trifluoromethoxy)phenyl)magnesium bromide according to general procedure H

(0.40 mmol scale), provided 4j (0.14 mmol, 41 mg, 34%) as a light-yellow oil. Rf =

0.44 (hexane, UV, KMnO4, PAA). Rf = 0.3 (hexane/EtOAc 90:10, UV, KMnO4, PAA)

1H NMR (400 MHz, Chloroform-d) δ 7.41 – 7.37 (m, 1H), 7.14 (d, J = 8.1 Hz, 1H),

5.98 (dq, J = 4.0, 1.9 Hz, 1H), 4.03 (s, 2H), 2.64 (tq, J = 6.5, 2.1 Hz, 1H), 2.50 – 2.44

(m, 1H), 1.92 ppm (t, J = 6.4 Hz, 1H). 13C NMR (101 MHz, Chloroform-d) δ 148.1,

140.2, 135.2, 126.5, 122.7, 123.52 – 109.58 (m), 120.6, 107.6, 64.5, 36.1, 31.3, 26.8 ppm.

LRMS (EI pos): m/z (%): 300.1 (15), 285.1 (2), 270.1 (1). HRMS (ESI-Quadrupole): m/z: calcd

for C15H15O3F3+: 300.0973; found: 300.0968. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 2943 (w),

29 B. Guo; G. Schwarzwalder; J. T. Njardarson, Angew. Chem. Int. Ed. 2012, 51, 5675.

29

2925 (w), 2889 (w), 2881 (w), 1509 (m), 1373 (w), 1260 (vs), 1212 (s), 1161 (s), 1118 (m),

1060 (m), 1027 (m), 1017 (w), 945 (w), 932 (w), 921 (w), 872 (w), 848 (m), 803 (w).

trans-(2R,3R)-2-(4-Fluorophenyl)-3-phenyloxirane (5a)

Using potassium (E)-trifluoro(styryl)borate and (4-fluorophenyl)magnesium

bromide according to general procedure G (0.40 mmol scale), provided 5a

(0.22 mmol, 46 mg, 54%) as a yellow solid. Rf = 0.21 (hexane, UV, KMnO4, PAA).

1H NMR (400 MHz, Chloroform-d) δ 7.44 – 7.28 (m, 7H), 7.08 (tt, J = 8.8, 2.5 Hz,

2H), 3.85 ppm (dd, J = 9.4, 1.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-

d) δ 162.90 (d, J = 246.6 Hz), 137.0, 132.98 (d, J = 3.0 Hz), 128.7, 128.6, 127.31

(d, J = 8.3 Hz), 125.6, 115.70 (d, J = 21.7 Hz), 63.0, 62.4 ppm. LRMS (EI pos): m/z (%): 214.0

(20), 196.0 (20), 185.0 (100), 165.0 (70), 157.0 (10), 133.0 (10), 123.0 (30), 107.0 (35), 89.0

(35), 77.0 (25), 63.0 (20), 51.0 (20). Analytical data in accordance to literature.30

trans-(2R,3R)-2-Phenyl-3-(4-(trifluoromethoxy)phenyl)oxirane (5b)

Using potassium (E)-trifluoro(styryl)borate and (4-

(trifluoromethoxy)phenyl)magnesium bromide according to general procedure

G (0.40 mmol scale), provided 5b (0.19 mmol, 53 mg, 47%) as a yellow solid.

Rf = 0.14 (hexane, UV, KMnO4, PAA). 1H NMR (400 MHz, Chloroform-

d) δ 7.36 – 7.29 (m, 7H), 7.20 (d, J = 8.0 Hz, 2H), 3.82 ppm (dd, J = 19.7,

1.9 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 149.3, 136.8, 136.0, 128.8,

128.7, 127.0, 125.6, 122.4, 120.58 (q, J = 257.3 Hz), 63.1, 62.2 ppm. LRMS (EI pos): m/z (%):

280.1 (30), 262.1 (15), 251.1 (100), 189.0 (35), 165.1 (85), 152.1 (20), 105.0 (30), 89.1 (40),

77.0 (45), 63.0 (20), 51.0 (20). HRMS (ESI-Quadrupole): m/z: calcd for C15H11F3O2+: 280.0711;

found: 279.0627. IR (Diamond-ATR, neat) ��𝑚𝑎𝑥 (cm-1): 3073 (w), 3039 (w), 2988 (w), 2426

(vw), 1978 (vw), 1913 (vw), 1779 (vw), 1596 (vw), 1509 (m), 1500 (w), 1462 (w), 1430 (w),

1254 (s), 1217 (s), 1199 (s), 1170 (vs), 1112 (m), 1101 (m), 1092 (m), 1071 (m), 1027 (m),

1017 (m), 1000 (m), 951 (m), 921 (m), 884 (m), 861 (m), 851 (m), 833 (s), 826 (s), 794 (m),

770 (w), 748 (s), 729 (m), 699 (s), 673 (m). Mp (°C) = 58.

30 T. Niwa; M. Nakada, J. Am. Chem. Soc. 2012, 134, 13538–13541.

30

3. NMR Spectra

1H NMR (400 MHz, Acetonitrile-d3)

Potassium trifluoro(4-(trimethylsilyl)phenyl)borate (SM1)


Potassium trifluoro(6-methoxynaphthalen-2-yl)borate (SM2)

1H

31

NMR (400 MHz, Acetone-d6)

Potassium trifluoro(2-methoxy-5-pyridinyl)borate (SM3)

32


Potassium trifluoro(2-methylquinolin-6-yl)borate (SM4)

33


Potassium trifluoro(4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)phenyl)borate

(SM5)

34

1H NMR (400 MHz, Acetone-d6)

Potassium trifluoro(4-iodophenyl)borate (SM6)

35

1H NMR (400 MHz, Acetonitrile-d3) and 13C NMR (101 MHz, Acetonitrile-d3)

Potassium tris(4-fluorophenyl)(4-methoxyphenyl)borate (1a)

36

1H NMR (400 MHz, Acetone-d6) and 13C NMR (101 MHz, Acetone-d6)

(E)-tris(4-fluorophenyl)(styryl)borate (3a)

37

1H NMR (400 MHz, Acetone-d6) and 13C NMR (101 MHz, Acetone-d6)

Potassium (E)-tris(4-fluorophenyl)(styryl)borate (3b)

38

1H NMR (400 MHz, Chloroform-d)

4-Fluoro-4'-methoxy-1,1'-biphenyl (2a)


1,1´-Biphenyl (2b)

39


4-Methoxy-4'-(trifluoromethoxy)-1,1'-biphenyl (2c)


4-Methyl-4'-(trifluoromethoxy)-1,1'-biphenyl (2d)

40

1H NMR (400 MHz, Chloroform-d) and 13C NMR (101 MHz, Chloroform-d)

Trimethyl(4'-(trifluoromethoxy)-[1,1'-biphenyl]-4-yl)silane (2e)

41


(3',5'-Bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)trimethylsilane (2f)

42


4'-phenoxy-3,5-bis(trifluoromethyl)-1,1'-biphenyl (2g)

43


4-Phenoxy-4'-(trifluoromethoxy)-1,1'-biphenyl (2h)

44


5-(3,5-Dimethylphenyl)benzo[d][1,3]dioxole (2i)

45


2-(4-Fluorophenyl)-6-methoxynaphthalene (2j)

46


4'-Fluoro-[1,1'-biphenyl]-3-ol (2k)

47


4'-(Trifluoromethoxy)-[1,1'-biphenyl]-3-ol (2l)

48


N,N-Diisopropyl-4'-phenoxy-[1,1'-biphenyl]-4-carboxamide (2m)

49


4'-Phenoxy-[1,1'-biphenyl]-4-carbonitrile (2n)

50


5-(3,5-Bis(trifluoromethyl)phenyl)benzo[c][1,2,5]oxadiazole (2o)

51


5-(4-(Trifluoromethoxy)phenyl)benzo[c][1,2,5]oxadiazole (2p)

52


5-(4-Fluorophenyl)benzo[c][1,2,5]oxadiazole (2q)

53


2-(4-Fluorophenyl)benzofuran (2r)

54


5-(3,5-Bis(trifluoromethyl)phenyl)-2-methoxypyridine (2s)

55


6-(4-Fluorophenyl)-2-methylquinoline (2t)

56


2-(p-Tolyl)dibenzo[b,d]furan (2u)

57


1-(3',5'-Bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)-5-(p-tolyl)-3-(trifluoromethyl)-1H -pyrazole (2v)

58


4-Iodo-4'-(trifluoromethoxy)-1,1'-biphenyl (2w)

59


4-Bromo-4'-(trifluoromethoxy)-1,1'-biphenyl (2x)

60


4-Chloro-4'-iodo-3-(trifluoromethyl)-1,1'-biphenyl (2y)

61


2-(4-Iodophenyl)dibenzo[b,d]furan (2z)

62


4'-Fluoro-[1,1'-biphenyl]-4-carbonitrile (2aa)


4'-(Trifluoromethoxy)-[1,1'-biphenyl]-4-carbonitrile (2ab)

63


(E)-1-Fluoro-4-styrylbenzene (4a)


(E)-4-(4-Fluorostyryl)-1,1'-biphenyl (4b)

64


(E)-1-Styrylnaphthalene (4c)


(E)-1,2-Diphenylethene (4d)

65


(E)-1-Chloro-3-styrylbenzene (4e)


4'-Fluoro-2,3,4,5-tetrahydro-1,1'-biphenyl (4f)

66


4-Phenyl-3,6-dihydro-2H-pyran (4g)


4-(3,5-Bis(trifluoromethyl)phenyl)-3,6-dihydro-2H-pyran (4h)

67


4-(3,5-Dimethylphenyl)-3,6-dihydro-2H-pyran (4i)

68


8-(4-(Trifluoromethoxy)phenyl)-1,4-dioxaspiro[4.5]dec-7-ene (4j)

69


trans-(2R,3R)-2-(4-Fluorophenyl)-3-phenyloxirane (5a)

70


trans-(2R,3R)-2-Phenyl-3-(4-(trifluoromethoxy)phenyl)oxirane (5b)

71

4. Calculations

Table S7 – Equilibrium structure of anion 1a and initial structure of radical [1a·] (in Angstrom).

Atom X Y Z

1 C -0.7188616463 1.0853680749 -0.9426413464

2 C -1.9396952872 0.7636842786 -1.5757905192

3 C -0.2046352690 2.3603777141 -1.2440495396

4 C -2.5980608162 1.6277057538 -2.4545698702

5 H -2.3990275309 -0.1995658094 -1.3647187347

6 C -0.8397703918 3.2539703774 -2.1151635278

7 H 0.7250634325 2.6783629779 -0.7802640162

8 C -2.0303843038 2.8686403360 -2.7110348757

9 H -3.5369236959 1.3562862392 -2.9304818630

10 H -0.4247260176 4.2356948241 -2.3291032940

11 C -1.1464248130 -0.6308675531 1.0724393463

12 C -1.2752602965 -1.9967500633 1.3869167037

13 C -2.0835215061 0.2217786920 1.6964947484

14 C -2.2511809723 -2.4906446679 2.2609414766

15 H -0.5942068657 -2.7092120671 0.9295332843

16 C -3.0669508140 -0.2353968179 2.5778122243

17 H -2.0486681879 1.2868147466 1.4769866606

18 C -3.1332630332 -1.5959441993 2.8465471744

19 H -2.3340585839 -3.5512952397 2.4846188094

20 H -3.7772014550 0.4411586573 3.0462987538

21 C 0.7216765304 -1.2247976761 -0.8214453420

22 C 1.6538997166 -2.0972914428 -0.2289653256

23 C 0.4491842176 -1.4889168161 -2.1792406277

24 C 2.2639298981 -3.1600087942 -0.9073872981

25 H 1.9289804679 -1.9398780146 0.8122956841

26 C 1.0425740032 -2.5345246173 -2.8863123716

27 H -0.2494839778 -0.8493221722 -2.7122508709

28 C 1.9545756580 -3.3814571173 -2.2515002945

29 H 2.9739062508 -3.7920473303 -0.3821199723

30 H 0.8140324584 -2.7083947612 -3.9353783752

31 C 1.2099559997 0.7293805440 0.9490508810

32 C 2.4356093483 1.0824722947 0.3420270316

33 C 1.0980141432 1.0615836877 2.3120761075

34 C 3.4688153147 1.7310792949 1.0233210184

72

35 H 2.5916021673 0.8304404276 -0.7047710710

36 C 2.1147864075 1.7058064833 3.0276825399

37 H 0.1868796720 0.8042492588 2.8452905589

38 C 3.2876327439 2.0341794575 2.3662595660

39 H 4.4030136771 1.9938959055 0.5335152020

40 H 2.0061858228 1.9479885357 4.0818989844

41 B 0.0173016030 -0.0111346299 0.0630486884

42 F -2.6629601303 3.7285266072 -3.5624021993

43 O 2.4934180441 -4.3912188476 -3.0292137199

44 C 3.4181516795 -5.2595616460 -2.4154066578

45 H 3.7222853344 -5.9768401204 -3.1832723099

46 H 2.9733659900 -5.8063684304 -1.5705307800

47 H 4.3084240835 -4.7249332595 -2.0518300132

48 F 4.2894919240 2.6622727133 3.0493736805

49 F -4.0918704939 -2.0614390887 3.7004144912

Table S8 – Geometry of radical 6 (in Angstrom).

Atom X Y Z

1 C -0.9061929564 0.9986008413 -1.0508253688

2 C -1.5483277419 0.4793716268 -2.1913060217

3 C -1.0695292466 2.3782785887 -0.8232465923

4 C -2.2939219277 1.2746247867 -3.0645135781

5 H -1.4725904129 -0.5845137126 -2.4077245426

6 C -1.8082693862 3.2006948341 -1.6765186353

7 H -0.6093763570 2.8319029563 0.0522325026

8 C -2.4096145470 2.6309299153 -2.7910308398

9 H -2.7819329130 0.8601095870 -3.9415588791

10 H -1.9236967984 4.2639741515 -1.4888035473

11 C -1.1966998756 -0.4937973661 1.1360820070

12 C -1.9541121972 -1.6657128477 0.9468960248

13 C -1.4959435983 0.2557036975 2.2896330535

14 C -2.9365092382 -2.0830637709 1.8479004626

15 H -1.7816512487 -2.2749944102 0.0617948613

16 C -2.4710754290 -0.1340478723 3.2101746769

17 H -0.9542508399 1.1801255398 2.4792739703

18 C -3.1775827896 -1.3058805549 2.9727409707

19 H -3.5120978074 -2.9899927231 1.6884436657

20 H -2.6886716494 0.4538766153 4.0968128647

73

21 C 0.7839048983 -1.1362775235 -0.6612231392

22 C 1.1090768998 -2.3333022622 0.0386734994

23 C 1.3617831400 -0.9941647223 -1.9593394297

24 C 1.8238786408 -3.3671197461 -0.5434049228

25 H 0.7369509882 -2.4634551925 1.0496961392

26 C 2.0762260231 -2.0091385039 -2.5564383172

27 H 1.1821348249 -0.0789658095 -2.5138671153

28 C 2.3140862064 -3.2137868753 -1.8555153888

29 H 2.0013906787 -4.2799123765 0.0139683595

30 H 2.4686259412 -1.9153650679 -3.5643338151

31 C 1.2532845282 0.6813824584 0.6397783766

32 C 2.0235508712 1.6284434021 -0.0859488571

33 C 1.7526817416 0.2893964533 1.9101986748

34 C 3.1454430224 2.2365377030 0.4607383965

35 H 1.6982964524 1.9236342871 -1.0781161895

36 C 2.8723649687 0.8851341330 2.4750983271

37 H 1.2145833028 -0.4611413745 2.4798508900

38 C 3.5533261482 1.8546271102 1.7388925496

39 H 3.7087964250 2.9923335775 -0.0772287615

40 H 3.2281174796 0.6172080637 3.4649084433

41 B -0.1463042373 0.0344465763 0.0138278403

42 F -3.1251151347 3.4165940738 -3.6311698366

43 O 3.0244902542 -4.1443609083 -2.5230031749

44 C 3.3244956024 -5.3842206803 -1.8831625229

45 H 3.8945250663 -5.9602164442 -2.6126794004

46 H 2.4078605730 -5.9256295094 -1.6222798038

47 H 3.9303639190 -5.2279442565 -0.9833173545

48 F 4.6418210318 2.4329946034 2.2746865242

49 F -4.1229727957 -1.7000143717 3.8592517534

Table S9 – Geometry of [TS]# (in Angstrom).

Atom X Y Z

1 C -0.9783567395 0.9741016873 -1.0898796894

2 C -1.6471228502 0.5866999752 -2.2673505299

3 C -0.9789506325 2.3477841116 -0.7846509396

4 C -2.2830540504 1.5083594372 -3.1015130381

5 H -1.6770750082 -0.4651231124 -2.5435252023

6 C -1.5983383094 3.2913051719 -1.6052758784

74

7 H -0.4740787318 2.6998407101 0.1114480787

8 C -2.2449187909 2.8521803456 -2.7541397024

9 H -2.7980893468 1.2009100939 -4.0062767382

10 H -1.5888521703 4.3503393863 -1.3667958349

11 C -1.3082628446 -0.5530482767 1.1161865397

12 C -1.9293050028 -1.8155008387 1.1696817567

13 C -1.6422572800 0.3595095861 2.1359019914

14 C -2.8277256802 -2.1629032050 2.1816511973

15 H -1.7153646554 -2.5496653552 0.3966253536

16 C -2.5206845671 0.0334475127 3.1678425810

17 H -1.2035151796 1.3541347905 2.1299025762

18 C -3.1026705351 -1.2295902905 3.1713258736

19 H -3.3083113346 -3.1358401901 2.2114354845

20 H -2.7657401736 0.7388685841 3.9557186276

21 C 0.7570218937 -1.0974148178 -0.6186534269

22 C 1.0695980383 -2.3799154068 0.0273355027

23 C 1.2721061461 -1.0077726367 -1.9962746274

24 C 1.8583168079 -3.3477407895 -0.5567435841

25 H 0.6616240166 -2.5764928894 1.0122361861

26 C 2.0475423059 -1.9808821883 -2.5633507639

27 H 0.9980959039 -0.1441146672 -2.5920597589

28 C 2.3791769395 -3.1616596034 -1.8528658966

29 H 2.0516817477 -4.2653972767 -0.0111425685

30 H 2.4042815454 -1.8843839532 -3.5850077259

31 C 1.4705782360 0.2179778428 0.3757335090

32 C 2.1300153989 1.2735193063 -0.2773869478

33 C 1.7460636066 -0.0018280355 1.7369537370

34 C 3.0158457170 2.1021328153 0.4053101443

35 H 1.9481955965 1.4591362488 -1.3294040682

36 C 2.6260830641 0.8189705751 2.4357586728

37 H 1.2556782073 -0.8096602517 2.2673972998

38 C 3.2514339775 1.8591403525 1.7549472833

39 H 3.5238338445 2.9230874535 -0.0902511622

40 H 2.8328565818 0.6645153024 3.4897808106

41 B -0.3982062810 -0.1619851407 -0.1318501792

42 F -2.8495854697 3.7578611438 -3.5557545479

43 O 3.1679019577 -4.0485775613 -2.5167517309

44 C 3.5158028552 -5.2643168132 -1.8691082005

75

45 H 4.1515730311 -5.8054342899 -2.5717779379

46 H 2.6271353636 -5.8679838562 -1.6441139989

47 H 4.0729614101 -5.0797558158 -0.9416714120

48 F 4.1108786073 2.6517245409 2.4210269176

49 F -3.9601971664 -1.5546532120 4.1643752674

Table S10 – Geometry of radical 7 (in Angstrom).

Atom X Y Z

1 C -1.0325720041 1.0888015728 -0.8841318199

2 C -2.3988149027 1.1153398835 -1.2516875262

3 C -0.2626021293 2.2156520826 -1.2585961397

4 C -2.9682897081 2.1808237358 -1.9455600314

5 H -3.0305944792 0.2699114960 -0.9989172697

6 C -0.8104430507 3.2983604871 -1.9402715943

7 H 0.7889878785 2.2569379673 -0.9996154655

8 C -2.1602592218 3.2618152202 -2.2751042660

9 H -4.0153802174 2.1847729050 -2.2309924476

10 H -0.2141392689 4.1636669795 -2.2116298810

11 C -1.4695252632 -1.0581300599 0.6844880716

12 C -1.5335382341 -2.4663035255 0.6084348050

13 C -2.3536635160 -0.4289379433 1.5901621614

14 C -2.4254899058 -3.2074901289 1.3823890928

15 H -0.8914548799 -2.9950555389 -0.0870489011

16 C -3.2263481680 -1.1523691957 2.4016610100

17 H -2.3522164003 0.6550025651 1.6695508595

18 C -3.2494303793 -2.5365095242 2.2783379933

19 H -2.4867556692 -4.2884750355 1.3051914091

20 H -3.8890109744 -0.6639836455 3.1089913746

21 C 1.1236750344 -0.5757199638 -0.2330884669

22 C 1.4807665004 -1.8395619294 0.5219685902

23 C 1.2718181164 -0.7984964966 -1.7230134450

24 C 1.8924823290 -3.0041932980 -0.0670244868

25 H 1.4382914016 -1.7861284504 1.6060806058

26 C 1.6282908232 -1.9974805744 -2.2783364011

27 H 1.0620161791 0.0420554283 -2.3761789687

28 C 1.9558487126 -3.1200701308 -1.4794320437

29 H 2.1543331132 -3.8473872941 0.5643733447

30 H 1.6901397695 -2.1091032276 -3.3576698008

76

31 C 2.0308358485 0.5456972739 0.3249244011

32 C 3.2044663193 0.9364207462 -0.3333670326

33 C 1.7298941533 1.1452402344 1.5576171833

34 C 4.0449421019 1.9126088896 0.2042176226

35 H 3.4633577011 0.4706665543 -1.2799981988

36 C 2.5599838230 2.1169741560 2.1145767964

37 H 0.8299530092 0.8499653854 2.0930555034

38 C 3.7073114813 2.4882437763 1.4227588688

39 H 4.9524866797 2.2243868406 -0.3030411813

40 H 2.3298954009 2.5867876441 3.0654184060

41 B -0.4643368939 -0.1725110851 -0.1338415718

42 F -2.6977210068 4.3045307795 -2.9387208209

43 O 2.3226430111 -4.2438659332 -2.1583640677

44 C 2.6784675960 -5.3997818344 -1.4154542301

45 H 2.9319543949 -6.1629818417 -2.1533480813

46 H 1.8430649023 -5.7560708604 -0.7983657119

47 H 3.5487076332 -5.2145003168 -0.7724095630

48 F 4.5152089939 3.4333179402 1.9507131223

49 F -4.1016166354 -3.2489662096 3.0452974937

77

5. Additional LED information

More detailed information about the used LEDs for setup 3 can be found in the attached data

sheet:

download fileview on ChemRxivSupporting_Didier_CRxiv.pdf (7.00 MiB)



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