Supplementary Materials for SUEMENTARY INRMATIN · Supplementary Materials for Conversion of...

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2417

Supplementary Materials for

Conversion of alkanes to linear alkylsilanes using an

iridium-iron-catalysed tandem

dehydrogenation-isomerisation-hydrosilylation

Xiangqing Jia1 and Zheng Huang1*

1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of

Science, 345 Lingling Road, Shanghai 200032, China

*E-mail: [email protected]

This PDF file includes:

Materials and Methods

Supplementary Table S1


References

NMR Spectra













References

NMR Spectra













References

NMR Spectra

S-1









Table of Contents:

1. General Information..……………………………………………………………………………………………..…...2

a. Materials……………………………………………………………………………………….…………………....2

b. Analytical methods………………………………………………………………………..…………….…………..2

2. Procedures for Table 1………………..……………………………………………………….……………………….2

Table S1 Evaluation of metal catalysts for tandem olefin isomerisation-hydrosilylation…………….…...…………..3

Table S2 Evaluation of the relative rates for isomerisation-hydrosilylation of 1-, 2-, or 3-octenes...…………………4

3. Procedures for Table 2………………………………………………………………………………………………….4

4. Procedures for Table 3………………………………………………………………………………………………….8

5. General procedures for preparation of the standard alkylboronates………………………………..…………..……....9

6. References……………………………………………………………………………………………………...……...11

7. NMR spectra for isolated compounds………………..……………………………...………………………………...12

© 2015 Macmillan Publishers Limited. All rights reserved



S-2

1. General information

a. Materials

All manipulations were carried out using standard Schlenk, high-vacuum and glovebox techniques. Toluene

and p-xylene were dried with Na and distilled under argon. n-Hexane was dried with CaH2 and distilled under

argon. Alkanes were dried with Na, vacuum transferred, and stored under argon. t-Butylethylene (TBE) was

purchased from TCI, and dried with LiAlH4, vacuum transferred, and stored under argon. (Me3SiO)2MeSiH

(MD’M) and Et2SiH2 were purchased from TCI. Both silanes were dried with CaH2, and distilled under argon.

Pinacolborane (HBPin) was purchased from TCI and purified according to the reported procedure1. Other

reagents were purchased from commercial suppliers and used without further purification. (PSCOP)IrHCl (1)2,

(PNN)FeCl2 (2a)3, (iPrPDI)FeBr2 (2b)4, (EtPDI)FeBr2 (2c)5 and (MePDI)FeBr2 (2d)4 were prepared as previously

reported.

b. Analytical methods

NMR spectra were recorded on Varian 300 or 400 MHz spectrometers and Agilent 400 MHz spectrometers

at ambient temperature. The residual peak of deuterated solvent was used as a reference for 1H and 13C

chemical shifts. GC analysis was acquired on Agilent 7820A gas chromatograph equipped with a

flame-ionization detector. GC-MS analysis was performed on Agilent 7890A gas chromatograph coupled to an

Agilent 5975C inert mass selective detector. High resolution mass spectrometer (HRMS) was performed by

the Analytical Laboratory of Shanghai Institute of Organic Chemistry (CAS).

2. Procedures for Table 1

Entry 1: In an argon-filled glovebox, a vial (10 mL) was charged with (PSCOP)IrHCl (1) (0.5 mol%),

NaBHEt3 (1.0 mol%), n-hexane (1.0 mL), trans-3-octene (0.2 mmol), MD’M (0.2 mmol). The reaction

mixture was stirred at room temperature for 12 h. After that, the reaction was quenched by exposing the

solution to air. Mesitylene (10 µL) was then added as internal standard. An aliquot was removed from the vial

and analyzed by GC. Primary octylsilane 6a was not detected by GC, and two branched octylsilanes resulting

from the hydrosilylation of trans-3-octene (6% yield) were detected.

Entries 2-5: In an argon-filled glovebox, a vial (10 mL) was charged with Fe-precatalyst (2a, 2b, 2c or 2d,

5.0 mol%), n-hexane (1.0 mL), trans-3-octene (0.2 mmol), MD’M (0.2 mmol), NaBHEt3 (10.0 mol%). The




S-3

reaction mixture stirred at room temperature for 12 h. After that, the reaction was quenched by exposing the


and analyzed by GC.

Entries 6-7: In an argon-filled glovebox, a vial (10 mL) was charged with (PSCOP)IrHCl (1) (0.5 mol%),

Fe-precatalyst (2c or 2d, 5.0 mol%), n-hexane (1.0 mL), trans-3-octene (0.2 mmol), MD’M (0.2 mmol),

NaBHEt3 (11.0 mol%). The reaction mixture was stirred at room temperature for 12 h. After that, the reaction

was quenched by exposing the solution to air. Mesitylene (10 µL) was then added as internal standard. An

aliquot was removed from the vial and analyzed by GC.

The effect of diene on Fe-catalyzed olefin isomerisation-hydrosilylation

In an argon-filled glovebox, a vial (10 mL) was charged with (PSCOP)IrHCl (1) (0.5 mol%), Fe-precatalyst

2c (5.0 mol%), p-xylene (1.0 mL), (E)-deca-1,3-diene (27 mol%), trans-3-octene (0.2 mmol), MD’M (0.2

mmol), NaBHEt3 (11.0 mol%). The reaction mixture was stirred for 12 h at room temperature. After that, the

reaction was quenched by exposing the solution to air, and mesitylene (10 µL) was added as internal standard.

An aliquot was removed from the vial and analyzed by GC and GC-MS, which showed the reaction did not

form any detectable alkylsilanes. The results suggest that dienes can inhibit Fe-catalyzed olefin

isomerization-hydrosilylation, presumably through chelation on the iron center.

Table S1. Evaluation of metal catalysts for tandem olefin isomerisation-hydrosilylation

+(Me3SiO)2MeSiH

5 mol% precat. NaBHEt3n-hexanert, 12 h

SiMe(OSiMe3)2nC6H13

6a4

Entry Precat. NaBHEt3[mol%]

Yield [%]a

of 6a1 2a 10 132 2b 10 4

3 2c 10 86

4 2d 10 86

5

6

7

2e 10 23(5)

1/2 [Ir(cod)Cl]2/dppp 0 8(2)

1/2 [Rh(cod)Cl]2/dppp 0 NR

NNtBu2P Fe

ClCl

NN NFe

ArAr BrBr

2a

2b, Ar = 2,6-iPr-C6H32c, Ar = 2,6-Et-C6H32d, Ar = 2,6-Me-C6H3

8 10 NRFeBr2

9 10 NRFeBr2/dppp

NN NCo

ArAr ClCl

2e, Ar = 1,3,5-Me-C6H2

S-3



and analyzed by GC.















+(Me3SiO)2MeSiH


SiMe(OSiMe3)2nC6H13

6a4


Yield [%]a

of 6a1 2a 10 132 2b 10 4

3 2c 10 86

4 2d 10 86

5

6

7

2e 10 23(5)

1/2 [Ir(cod)Cl]2/dppp 0 8(2)


NNtBu2P Fe

ClCl

NN NFe

ArAr BrBr

2a


8 10 NRFeBr2

9 10 NRFeBr2/dppp

NN NCo

ArAr ClCl

2e, Ar = 1,3,5-Me-C6H2

S-3



and analyzed by GC.















+(Me3SiO)2MeSiH


SiMe(OSiMe3)2nC6H13

6a4


Yield [%]a

of 6a1 2a 10 132 2b 10 4

3 2c 10 86

4 2d 10 86

5

6

7

2e 10 23(5)

1/2 [Ir(cod)Cl]2/dppp 0 8(2)


NNtBu2P Fe

ClCl

NN NFe

ArAr BrBr

2a


8 10 NRFeBr2

9 10 NRFeBr2/dppp

NN NCo

ArAr ClCl

2e, Ar = 1,3,5-Me-C6H2

S-4

a Determined by GC using mesitylene as an internal standard. Numbers in the parenthesis are yields of branched products.

Table S2. Evaluation of the relative rates for isomerisation-hydrosilylation of 1-, 2-, and 3-octenes

a Determined by GC using mesitylene as an internal standard

3. General procedures for Table 2

Reactions in neat alkanes (entries 1-5 and entries 12-15): In an argon-filled glovebox, a thick-wall

Kontes flask (10 mL) was charged with (PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), alkane (2.0 mL)

and TBE (0.50 mmol). The flask was sealed with a Teflon plug under an argon atmosphere, and the solution

stirred in a 200 °C oil bath for allotted time. After that, the flask was cooled to room temperature, and

(EtPDI)FeBr2 (2c) (10.0 mol%), MD’M or Et2SiH2 (0.50 mmol), NaBHEt3 (20.0 mol%) were added to the

solution in an argon-filled glovebox. The flask was then sealed with a Teflon plug under an argon atmosphere,

and the solution continued to stir for 12 h at room temperature. The reaction was then quenched by exposing

the solution to air, and mesitylene (20 µL) was then added as internal standard. An aliquot was removed from

the vial and analyzed by GC. Elution of the resulting solution through a silica gel plug with n-hexane afforded

the crude products, which typically include the desired product, the side-product resulting from hydrosilylation

of unreacted t-butylethylene (TBE), and the unreacted alkane substrate. The crude products were further

purified by removal of the side-product and unreacted substrate by evaporation under reduced pressure to

afford the pure alkane silylation product.

Reactions in p-xylene (entries 6-11, and 16): In an argon-filled glovebox, a thick-wall Kontes flask (10

mL) was charged with (PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), p-xylene (2.0 mL), alkane [1.5




S-4

a Determined by GC using mesitylene as an internal standard. Numbers in the parenthesis are yields of branched products.

Table S2. Evaluation of the relative rates for isomerisation-hydrosilylation of 1-, 2-, and 3-octenes

a Determined by GC using mesitylene as an internal standard

3. General procedures for Table 2

Reactions in neat alkanes (entries 1-5 and entries 12-15): In an argon-filled glovebox, a thick-wall

Kontes flask (10 mL) was charged with (PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), alkane (2.0 mL)

and TBE (0.50 mmol). The flask was sealed with a Teflon plug under an argon atmosphere, and the solution

stirred in a 200 °C oil bath for allotted time. After that, the flask was cooled to room temperature, and

(EtPDI)FeBr2 (2c) (10.0 mol%), MD’M or Et2SiH2 (0.50 mmol), NaBHEt3 (20.0 mol%) were added to the

solution in an argon-filled glovebox. The flask was then sealed with a Teflon plug under an argon atmosphere,

and the solution continued to stir for 12 h at room temperature. The reaction was then quenched by exposing

the solution to air, and mesitylene (20 µL) was then added as internal standard. An aliquot was removed from

the vial and analyzed by GC. Elution of the resulting solution through a silica gel plug with n-hexane afforded

the crude products, which typically include the desired product, the side-product resulting from hydrosilylation

of unreacted t-butylethylene (TBE), and the unreacted alkane substrate. The crude products were further

purified by removal of the side-product and unreacted substrate by evaporation under reduced pressure to


Reactions in p-xylene (entries 6-11, and 16): In an argon-filled glovebox, a thick-wall Kontes flask (10

mL) was charged with (PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), p-xylene (2.0 mL), alkane [1.5




S-5

mmol except for entry 8 (2.5 mmol)] and TBE (0.50 mmol). The flask was sealed with a Teflon plug under an

argon atmosphere, and the solution stirred in a 200 °C oil bath for allotted time. After that, the flask was

cooled to room temperature, and (EtPDI)FeBr2 (2c) or (MePDI)FeBr2 (2d) (10.0 mol%), MD’M or Et2SiH2 (0.50

mmol), NaBHEt3 (20.0 mol%) were added to the solution in an argon-filled glovebox. The flask was then

sealed with a Teflon plug under an argon atmosphere, and the solution continued to stir for 12 h at room

temperature. The reaction was then quenched by exposing the solution to air, and mesitylene (20 µL) was then

added as internal standard. An aliquot was removed from the vial and analyzed by GC. The resulting solution

was concentrated under vacuum, and the residue was purified by elution through a silica gel plug with

n-hexane and removal of the side-product and unreacted substrate by evaporation under reduced pressure to


3-(3,3-dimethylbutyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane 1H NMR (400 MHz, CDCl3): δ 1.19-1.14 (m, 2

H), 0.84 (s, 9 H), 0.40-0.36 (m, 2 H), 0.09 (s, 18 H), -0.01 (s, 3 H). 13C{1H} NMR (101 MHz, CDCl3): δ 37.1,

31.0, 29.0, 12.0, 2.0, -0.4. The spectroscopic data correspond to the reported data6.

1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane (6a) 1H NMR (400 MHz, CDCl3): δ 1.26 (m, 12 H), 0.88 (t, J =

6.8 Hz, 3 H), 0.45 (vt, J = 7.5 Hz, 2 H), 0.08 (s, 18 H), -0.01 (s, 3 H). The spectroscopic data correspond to the

reported data7.

3-decyl-1,1,1,3,5,5,5-heptamethyltrisiloxane (6b) 1H NMR (400 MHz, CDCl3): δ 1.26 (m, 16 H), 0.88 (t, J =

6.7 Hz, 3 H), 0.44 (vt, J = 7.6 Hz, 2 H), 0.08 (s, 18 H), -0.01 (s, 3 H). 13C{1H} NMR (101 MHz, CDCl3): δ

33.5, 32.2, 29.9, 29.8, 29.6, 29.5, 23.3, 22.9, 17.8, 14.3, 2.0, -0.08. HRMS (EI), m/z calcd. for C16H39O2Si3

(M-CH3+) 347.2258, found: 347.2256.




S-6

3-hexyl-1,1,1,3,5,5,5-heptamethyltrisiloxane (6c) 1H NMR (400 MHz, CDCl3): δ 1.28 (m, 8 H), 0.89 (t, J =

6.9 Hz, 3 H), 0.45 (t, J = 7.7 Hz, 2H), 0.08 (s, 18 H), -0.01 (s, 3 H). 13C{1H} NMR (101 MHz, CDCl3): δ 33.3,

32.0, 23.4, 22.9, 17.9, 14.4, 2.05, -0.06. The spectroscopic data correspond to the reported data8.

1,1,1,3,5,5,5-heptamethyl-3-(6-methylheptyl)trisiloxane (6d) 1H NMR (400 MHz, CDCl3): δ 1.55-1.45 (m, 1

H), 1.35-1.21 (m, 6 H), 1.20-1.09 (m, 2 H), 0.86 (d, J = 6.6 Hz, 6 H), 0.45 (vt, J = 7.7 Hz, 2 H), 0.08 (s, 18 H),

-0.01 (s, 3 H). 13C{1H} NMR (101 MHz, CDCl3): δ 39.1, 33.7, 28.2, 27.3, 23.3, 22.8, 17.8, 2.0, -0.1. HRMS

(EI), m/z calcd. for C15H38O2Si3 (M-CH3+) 319.1945, found: 319.1941.

1,1,1,3,5,5,5-heptamethyl-3-(4-(trimethylsilyl)butyl)trisiloxane (6e) 1H NMR (400 MHz, CDCl3): δ

1.30-1.25 (m, 4 H), 0.49-0.43 (m, 4 H), 0.08 (s, 18 H), -0.01 (s, 3 H), -0.03 (s, 9 H). 13C{1H} NMR (101 MHz,

CDCl3): δ 27.8, 27.3, 17.6, 16.7, 2.03, -0.09, -1.45. HRMS (EI), m/z calcd. for C13H35O2Si4 (M-CH3+)

335.1714, found: 335.1716.

3-(4,4-dimethylpentyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane (6f) 1H NMR (400 MHz, CDCl3): δ 1.34-1.23

(m, 2 H), 1.23-1.15 (m, 2 H), 0.86 (s, 9 H), 0.46-0.37 (m, 2 H), 0.09 (s, 18 H), 0.00 (s, 3 H). 13C{1H} NMR

(101 MHz, CDCl3): δ 48.5, 30.7, 29.6, 18.7, 18.3, 2.1, 0.0.

1,1,1,3,5,5,5-heptamethyl-3-(3-phenylpropyl)trisiloxane (6g) 1H NMR (400 MHz, CDCl3): δ 7.30-7.27 (m, 2

H), 7.19-7.16 (m, 3 H), 2.62 (m, 2 H), 1.68-1.60 (m, 2 H), 0.53-0.49 (m, 2 H), 0.08 (s, 18 H), 0.00 (s, 3 H). 13C{1H} NMR (101 MHz, CDCl3): δ 142.9, 128.6, 128.4, 125.8, 39.6, 25.4, 17.6, 2.03, -0.08. The

spectroscopic data correspond to the reported data9.




S-7

3-(3-(4-methoxyphenyl)propyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane (6h) 1H NMR (400 MHz, CDCl3): δ

7.08 (d, J = 8.6 Hz, 2 H), 6.83 (d, J = 8.6 Hz, 2 H), 3.79 (s, 3 H), 2.58 -2.52 (t, J = 7.5 Hz, 2 H), 1.68-1.60 (m,

2 H), 0.53-0.45 (m, 2 H), 0.07 (s, 18 H), -0.01 (s, 3 H).

3-(3-(3-fluorophenyl)propyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane (6i) 1H NMR (400 MHz, CDCl3): δ

7.23 (m, 1 H), 7.07 (s, 1 H), 6.90-6.83 (m, 2 H), 2.61 (t, J = 7.6 Hz, 2 H), 1.71-1.57 (m, 2 H), 0.55-0.44 (m,

2H), 0.08 (s, 18H), 0.00 (s, 3 H). 19F NMR (376 MHz, CDCl3): δ -114.5.

diethyl(octyl)silane (7a) 1H NMR (400 MHz, CDCl3): δ 3.65-3.59 (m, 1 H), 1.39-1.17 (m, 12 H), 0.97 (t, J

= 7.9 Hz, 6 H), 0.88 (t, J = 6.8 Hz, 3 H), 0.62-0.54 (m, 6 H). The spectroscopic data correspond to the reported

data10.

Decyldiethylsilane (7b) 1H NMR (400 MHz, CDCl3): δ 3.65-3.59 (m, 1 H), 1.37-1.19 (m, 16 H), 0.97 (t, J =

7.9 Hz, 6 H), 0.88 (t, J = 6.8 Hz, 3 H), 0.62-0.53 (m, 6 H). 13C{1H} NMR (101 MHz, CDCl3): δ 33.6, 32.1,

29.8, 29.8, 29.5, 24.8, 22.9, 14.3, 10.8, 8.4, 3.0. HRMS (EI), m/z calcd. for C14H32Si (M+) 228.2273, found:

228.2276.

diethyl(hexyl)silane (7c) 1H NMR (400 MHz, CDCl3): δ 3.66-3.58 (m, 1 H), 1.35-1.25 (m, 8 H), 0.97 (t, J =

7.9 Hz, 6 H), 0.88 (t, J = 6.9 Hz, 3 H), 0.64 – 0.53 (m, 6 H). 13C{1H} NMR (101 MHz, CDCl3): δ 33.2, 31.8,

24.7, 22.8, 14.3, 10.8, 8.4, 3.0.




S-8

diethyl(6-methylheptyl)silane (7d) 1H NMR (400 MHz, CDCl3): δ 3.66-3.59 (m, 1 H), 1.56-1.45 (m, 1 H),

1.39-1.21 (m, 6 H), 1.20-1.09 (m, 2 H), 0.97 (t, J = 7.9 Hz, 6 H), 0.86 (d, J = 6.6 Hz, 6 H), 0.64-0.50 (m, 6 H). 13C{1H} NMR (101 MHz, CDCl3): δ 39.2, 33.9, 28.2, 27.3, 24.8, 22.8, 10.8, 8.4, 3.0. HRMS (EI), m/z calcd.

for C12H27Si (M+) 199.1882, found: 199.1890.

(3-(diethylsilyl)propyl)trimethylsilane (7e) 1H NMR (400 MHz, CDCl3): δ 3.66-3.57 (m, 1 H), 1.42-1.22

(m, 4 H), 0.97 (t, J = 7.9 Hz, 6 H), 0.65-0.53 (m, 4 H), 0.48 (t, J = 9.2 Hz, 2 H), -0.03 (s, 9 H). 13C{1H} NMR

(101 MHz, CDCl3): δ 28.7, 27.9, 16.6, 10.5, 8.4, 3.0, -1.5. HRMS (EI), m/z calcd. for C10H25Si2 (M+) 201.1495,

found: 201.1500.

4. Procedures for Table 3

Entries 1-4: In an argon-filled glovebox, a thick-wall Kontes flask (10 mL) was charged with

(PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), alkane (1.0 mL) and TBE (0.25 mmol). The flask was

sealed with a Teflon plug under an argon atmosphere, and the solution was stirred in a 200 °C oil bath for

allotted time. After that, the flask was cooled to room temperature, and (PNN)FeCl2 (2a) (10.0 mol%), HBPin

(0.25 mmol), NaBHEt3 (20.0 mol%) were then added to the solution in an argon-filled glovebox. The flask was

then sealed with a Teflon plug under an argon atmosphere, and the solution continued to stir for 12 h at room

temperature. The reaction was then quenched by exposing the solution to air, and mesitylene (10 µL) was then

added as internal standard. An aliquot was removed from the vial and analyzed by GC.

Entries 5 and 7: In an argon-filled glovebox, a thick-wall Kontes flask (10 mL) was charged with

(PSCOP)IrHCl (1) (1.0 mol%), NaOtBu (1.2 mol%), p-xylene (1.0 mL), alkane (0.75 mmol) and TBE (0.25

mmol). The flask was sealed with a Teflon plug under an argon atmosphere, and the solution was stirred in a

200 °C oil bath for allotted time. After that, the flask was cooled to room temperature, and (PNN)FeCl2 (2a)

(10.0 mol%), HBPin (0.25 mmol), NaBHEt3 (20.0 mol%) were added to the solution in an argon-filled

glovebox. The flask was then sealed with a Teflon plug under an argon atmosphere, and the solution continued

to stir for 12 h at room temperature. The reaction was then quenched by exposing the solution to air, and

mesitylene (10 µL) was then added as internal standard. An aliquot was removed from the vial and analyzed

by GC.

Entry 6: In an argon-filled glovebox, a thick-wall Kontes flask (10 mL) was charged with (PSCOP)IrHCl




S-9

(1) (1.0 mol%), NaOtBu (1.2 mol%), p-xylene (1.0 mL), 2,4-dimethylhexane (1.25 mmol) and TBE (0.25

mmol). The flask was sealed with a Teflon plug under an argon atmosphere, and the solution was stirred in a

200 °C oil bath for allotted time. After that, the flask was cooled to room temperature, and (PNN)FeCl2 (2a)

(10.0 mol%), HBPin (0.25 mmol), NaBHEt3 (20.0 mol%) were added to the solution in an argon-filled

glovebox. The flask was then sealed with a Teflon plug under an argon atmosphere, and the solution continued

to stir for 12 h at room temperature. The reaction was then quenched by exposing the solution to air, and

mesitylene (10 µL) was then added as internal standard. An aliquot was removed from the vial and analyzed

by GC.

5. General procedures for preparation of the standard alkylboronates (for measurements of

their GC response factors relative to mesitylene)

In an argon-filled glovebox, a vial (10 mL) was charged with (PNN)FeCl2 (2a) (0.5 mol%), n-hexane or

toluene (1.0 mL), HBPin (0.5 mmol), α-olefin (0.5 mmol), NaBHEt3 (1.0 mol%). The reaction mixture was

stirred for 2 h at room temperature. Then the reaction was quenched by exposing the solution to air. The

resulting solution was concentrated under vacuum and the residue was purified by elution through a silica gel

plug with n-hexane and ethyl acetate.

2-(3,3-dimethylbutyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 1H NMR (400 MHz, CDCl3): δ 1.28 (t, J =

8.6 Hz, 2 H), 1.24 (s, 12 H), 0.84 (s, 9 H), 0.71 (t, J = 8.6 Hz, 2 H). The spectroscopic data correspond to the

reported data3.

4,4,5,5-tetramethyl-2-octyl-1,3,2-dioxaborolane (8a) 1H NMR (400 MHz, CDCl3): δ 1.41-1.38 (m, 2 H),

1.29-1.26 (m, 10 H), 1.24 (m, 12 H), 0.87 (t, J = 6.9 Hz, 3 H), 0.76 (t, J = 7.8 Hz, 2 H). The spectroscopic data

correspond to the reported data11.




S-10

2-decyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8b) 1H NMR (400 MHz, CDCl3): δ 1.41-1.35 (m, 2 H),

1.31-1.17 (m, 26 H), 0.87 (t, J = 6.8 Hz, 3 H), 0.76 (t, J = 7.7 Hz, 2 H). 13C{1H} NMR (101 MHz, CDCl3): δ

82.9, 32.6, 32.1, 29.8, 29.7, 29.6, 29.5, 24.9, 24.1, 22.8, 14.3. The spectroscopic data correspond to the

reported data12.

2-hexyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8c) 1H NMR (400 MHz, CDCl3): δ 1.41-1.38 (m, 2 H),

1.31-1.26 (m, 6 H), 1.24 (s, 12 H), 0.87 (t, J = 6.9 Hz, 3 H), 0.76 (t, J = 7.7 Hz, 2 H). The spectroscopic data


trimethyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butyl)silane (8e) 1H NMR (400 MHz, CDCl3): δ 1.46-1.39 (m, 2 H), 1.32-1.26 (m, 2 H), 1.24 (s, 12 H), 0.77 (t, J = 7.7 Hz, 2 H),

0.49-0.45 (m, 2 H), -0.05 (s, 9 H). 13C{1H} NMR (101 MHz, CDCl3): δ 82.9, 28.1, 26.8, 24.9, 16.6, -1.53.

HRMS (EI), m/z calcd. for C13H29O2Si10B (M+) 255.2066, found: 255.2068.

4,4,5,5-tetramethyl-2-(3-phenylpropyl)-1,3,2-dioxaborolane (8g) 1H NMR (400 MHz, CDCl3): δ 7.30-7.27

(m, 2 H), 7.19-7.16 (m, 3 H), 2.60 (t, J = 7.6 Hz, 2 H), 1.75 (m, 2 H), 1.26 (s, 12 H), 0.85 (t, J = 8.0 Hz, 2 H). 13C{1H} NMR (101 MHz, CDCl3): δ 142.7, 128.6, 128.2, 125.6, 82.9, 38.7, 26.2, 24.9. The spectroscopic data





S-11

6. References

1. Shimada, S.; Batsanov, A. S.; Howard, J. A. K.; Marder, T. B. Angew. Chem., Int. Ed. 2001, 40, 2168.

2. Yao, W.; Zhang, Y.; Jia, X.; Huang, Z. Angew. Chem., Int. Ed. 2014, 53, 1390.

3. Zhang, L.; Peng, D.; Leng, X.; Huang, Z. Angew. Chem., Int. Ed. 2013, 125, 3764.

4. Small, B. L.; Brookhart, M.; Bennett, A. M. A. J. Am. Chem. Soc. 1998, 120, 4049.

5. Schmidt, R.; Welch, M. B.; Palackal, S. J.; Alt, H. G. J. Mol. Catal. A: Chem. 2002, 179, 155.

6. Firgo, H. A.; Weber, W. P. Organometallics 1982, 1, 649-653.

7. Peng, D.; Zhang, Y.; Du, X.; Zhang, L.; Leng, X.; Walter, M. D.; Huang, Z. J. Am. Chem. Soc. 2013, 135,

19154.

8. Greenhalgh, M. D.; Frank, D. J.; Thomas, S. P. Adv. Synth. Catal. 2014, 356, 584.

9. Bandari, R.; Buchmeiser, M. R. Catal. Sci. Technol. 2012, 2, 220.

10. Steiman, T. J.; Uyeda, C. J. Am. Chem. Soc. 2015, 137, 6104.

11. Lata, C. J.; Crudden, C. M. J. Am. Chem. Soc. 2010, 132, 131.

12. Atack, T. C.; Lecker, R. M.; Cook, S. P. J. Am. Chem. Soc. 2014, 136, 9521.

13. Yi, J.; Liu, J. H.; Liang, J.; Dai, J. J.; Yang, C. T.; Fu, Y.; Liu, L. Adv. Synth. Catal. 2012, 354, 1685.




S-12

7. NMR spectra for isolated compounds

1H NMR (400 MHz, CDCl3) for 6a




S-13

1H NMR (400 MHz, CDCl3) for 6b




S-14

13C NMR (101 MHz, CDCl3) for 6b




S-15

1H NMR (400 MHz, CDCl3) for 6c




S-16

1H NMR (400 MHz, CDCl3) for 6d




S-17

13C NMR (101 MHz, CDCl3) for 6d




S-18

1H NMR (400 MHz, CDCl3) for 6e




S-19

13C NMR (101 MHz, CDCl3) for 6e




S-20

1H NMR (400 MHz, CDCl3) for 6f




S-21

13C NMR (101 MHz, CDCl3) for 6f




S-22

1H NMR (400 MHz, CDCl3) for 6g




S-23

13C NMR (101 MHz, CDCl3) for 6g




S-24

1H NMR (400 MHz, CDCl3) for 7a




S-25

1H NMR (400 MHz, CDCl3) for 7b




S-26

13C NMR (101 MHz, CDCl3) for 7b




S-27

1H NMR (400 MHz, CDCl3) for 7c




S-28

1H NMR (400 MHz, CDCl3) for 7d




S-29

13C NMR (101 MHz, CDCl3) for 7d




S-30

1H NMR (400 MHz, CDCl3) for 7e




S-31

13C NMR (101 MHz, CDCl3) for 7e


Supplementary Materials for SUEMENTARY INRMATIN · Supplementary Materials for Conversion of...

Documents

Transcript of Supplementary Materials for SUEMENTARY INRMATIN · Supplementary Materials for Conversion of...