Photoelectrochemistryin Organic Synthesis

Photoelectrochemistry in Organic Synthesis

Reporter :Gao Shiquan (高师泉）Supervisor: Prof. Zhang Junliang

2020-12-25

1. Introduction1.1 Synthetic Organic Electrochemistry

1.2 Visible-Light Photoredox Catalysis

1.3 Photoelectrochemical Organic Synthesis

2. Photoelectrochemical Organic Synthesis 2.1 Electromediated Reaction with Photoredox Catalysis

2.1.1 Oxidation Reaction2.1.2 Reduction Reaction2.1.3 Redox Neutral Reaction

2.2 Electromediated Reaction involving Photo-induced Radical

2.3 Interfacial Photoelectrochemistry

3. Summary and Prospection

Contents

IntroductionSynthetic Organic Electrochemistry

undivided cell divided cell (“H” cell)

workingelectrode

counterelectrode

constant current (cc)constant voltage (cv)

reference electrode

Electrochemical Cells

Modes of Operation

S. R. Waldvogel et al. Chem. Sci., 2020, 11, 12386.

low surface area(graphite Pt)

high surface area(Ni foam RVC)

sacrificial anode (Zn Mg Al)

THF DCM Acetone Methanol MeCN DMA H2O8 9 21 33 38 38 80

more resistance less resistanceε

Electrodes

Solution

P. S. Baran et al. Acc. Chem. Res. 2020, 53, 72.

Redox-neutralReaction

OxidativeReaction

ReductiveReaction

Workingelectrode

Counterelectrode

Workingelectrode

R. D. Little et al. Chem. Soc. Rev., 2014, 43, 2492. 7

Mes-AcrIr[dFCF3ppy]2(bpy) Ru(bpy)3 4CzIPN Eosin Y

G. A. Molander et al. ACS Catal. 2017, 7, 2563. 8

Introduction

ReductiveReaction

OxidativeReaction

Redox NeutralReaction

Energy TransferReaction

Visible-Light Photoredox Catalysis

Ox•-

sub•+

subb•-

suba•+

• energy constrained• energy losses• equivalent oxidizing or reducing agent

• low conductivity of organic solvents • unselective redox processes• limited mediators potential

The limits of PRCThe limits of SOE

IntroductionPhotoelectrochemical Organic Synthesis

High selectivity/energy efficiencyAtom efficient Large redox window

redox energyfrom

photoexcitation

redox energyfrom

electrochemistry

J. P. Barham et al. Angew. Chem. Int. Ed. 2020, 59, 2. 10

CN9,10-dicyanoanthracene

phenothiazine (PTZ)

HOMO-4

HOMO-3

SOMO-4

SOMO-1

HOMO-4

SOMO-1

HOMO-2

SOMO-2

HOMO-1

LUMO-2

HOMO-1

E = +0.70 V

E = 2.23 eV

Imax = 514, 772,864 nm

*E = 2.9 V

Imax = 450, 480,510 nm

*E = -3.2 V

E = 2.43 eV

E = -0.82 V

electromediatedphotoredox calatlyst (e-PRC)

SOMO-HOMO inversion SOMO-HOMO inversion

J.-C. Moutet, G. Reverdy. Tetrahedron Lett. 1979, 20, 2389. J.-C. Moutet, G. Reverdy. J. Chem. Soc. Chem. Commun. 1982, 654. 11

PTZ (6 mol%)LiClO4

Pt rotating disk voltammetry0.79 V vs SCE

Hg Lamp (<400 nm)MeCN

1:1.3 by HPLC

(DPE)NH

phenothiazine (PTZ)1 2

*TPPD•+

TPPD•+

OH OH O

Contents

Photoelectrochemical Organic Synthesis Electromediated Reaction with Photoredox Catalysis

B. Konig et al. Photochem. Photobiol. Sci., 2010, 9, 1367.B. Konig et al. Chem. Eur. J. 2008, 14, 1854.D. R. Carbery et al. Angew.Chem. Int.Ed. 2015, 54,8997.B. Konig et al. ChemCatChem. 2012, 4, 620.J. C. Gonzalez-Gomez et al. Organic Letters 2019 21 (5), 1368.

Flavin

B. Konig et al. Chem. Eur. J. 2008, 14, 1854.S. Lin et al. Angew. Chem. Int. Ed. 2020, 59, 409.

1a: E ≈ 1.5 V1b: E > 1.9 VRFT*: E = 1.67 V

Fluorescence quenching of RFT with 1a Fluorescence quenching of RFT with 1b

S. Lin et al. Angew. Chem. Int. Ed. 2020, 59, 409.

13C NMR of (A) TU-1-O2 (B) white precipitate (C) TU-1

Fluorescence quenching of RFT with TU-2

S. Lin et al. Angew. Chem. Int. Ed. 2020, 59, 409. 16

1b (1 eq.), RFT (5 mol%)LiOTf (0.1 M CH3CN), H2O

C(+)/Pt(-), 2.5 Vblue LED, 22 °C, 1 h

1b (1 eq.)RFT (5 mol%), TU-2 (10 mol%)

LiOTf (0.1 M CH3CN), H2OC(+)/Pt(-), 2.5 V

blue LED, 22 °C, 1 h

Z:E = 6:1 71% recovered, Z:E = 10:1100% 1b recovered

75% recovered, Z:E = 1:100100% 1b recovered

Z:E = 6:1

S. Lin et al. Angew. Chem. Int. Ed. 2020, 59, 409. 17

AcOOAc

Selected Substrates

H+RFT-H2

RFTRFT*

RFT•-H

OHtBu OtBu

RNS NR

E 0.8 V

96% 89%88%

T. H. Lambert et al. Angew. Chem. Int. Ed. 2019, 58, 13318. 18

Selected Substrates

65% 42% 75% 71%

T. H. Lambert et al. J. Am. Chem. Soc. 2020, 142, 1698. 19

Selected Substrates

*TAC2+

Me MeMe

SO2Ph HNN

89%72%40%80%

H.-C. Xu et al. Angew. Chem. Int. Ed. 2019, 58,4592. 20

Selected Substrates

Mes-Acr•

*Mes-Acr+

Mes-Acr+

F3B Me

Me+ BF3

Mes-Acr+ Mes-Acr•NH

E = 2.06 VEp/2 = -1.19 V

Ep/2 = -0.57 V

H.-C. Xu et al. Angew. Chem. Int. Ed. 2020, 59, 10626. 21

Selected Substrates

L. Ackermann. et al. Chem. Eur. J. 2020, 26, 3241. 22

Selected Substrates

79%with [Mes-Acr]ClO4

67%with [Ru(bpy)3](PF6)2

OMeCF3

71%with [Ru(bpy)3](PF6)2

64% (1:2 = 14:1)with [Mes-Acr]ClO4

A.-W. Lei et al. J. Am. Chem. Soc. 2020, 142, 17693. 23

Selected Substrates

S. Lin et al. J. Am. Chem. Soc. 2020,142, 2087. 24

Selected Substrates

*DCA•-

DCA•-

B2pin2Bpin

E = -3.2 V

E = -1.0 Ve-

T. H. Lambert et al. Angew. Chem. Int. Ed. 2020, 59, 658. 25

Selected Substrates

DDQ•-

E = 3.18 V

CHO N N

E = 1.5 V

DDQ•-

Electromediated Reaction involving Photo-induced RadicalPhotoelectrochemical Organic Synthesis

Selected Substrates

HCl (6 eq.)Et4NCl (0.3 eq.)C(+) Pt(-), 2 mAblue LED (10 W)

MeCN N

C(sp3)

+ H C(sp3)R1 R1

S. Stahl et al. Angew. Chem. Int. Ed. 2019, 58, 6385. 28

Selected Substrates

X.-L. Hu et al. Nat. Catal. 2019, 2, 366.

Interfacial Photoelectrochemistry

Photoelectrochemical Organic Synthesis

Selected Substrates

photoanode(semiconductor)

sub•+

VB:valence bandCB:conduction bandh:hole conduction

OMeNHN

•-H+

OMe -e-

E = 0.73 V

MeO CO2Me

87%(P1:P2=3:1)

77%o:p = 6:1

58%o:p = 14:1

C. P. Berlinguette et al. Nat. Commun. 2017, 8, 390. 30

Interfacial PhotoelectrochemistryPhotoelectrochemical Organic Synthesis

Contents

Summary and Prospection

OxidativeNMe

Reductive

4czIPN

TAC Mes-Acr

RFT TAC

Ru(bpy)3

9-fluorenone

• Rigorous control experiments• Interelectrode ohmic drop• Mass transfer

Summary and Prospection

The limits of Photoelectrochemistry

reactants

products

a:borosilicate glass coverb:working electrode platewith groove channelsc:ion-exchange membraned:counter electrode plate

New reaction ?New mediator ?Chiral reaction ?

Thanks for your kind attention

Photoelectrochemistryin Organic Synthesis

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