supporting information general remarks were collected · pdf filewere collected from the...

Supporting Information

General RemarksMost of chemicals were purchased from Sigma-Aldrich, Strem, Acros, TCI or Alfa, used as such unless stated otherwise and methyl benzylcarbamate was synthesized10. Solvents (Anhydrous and under inert atmosphere) were collected from The Solvent purification system by M BRAUN and used under standard schlenk technique. NMR spectra were recorded on Bruker Avance 300 and Bruker ARX 400 spectrometers. Chemical shifts (ppm) are given relative to solvent: references for CDCl3 were 7.26 ppm (1H NMR) and 77.00 ppm (13C NMR). Multiplets were assigned as s (singlet), d (doublet), t (triplet), q (quartet), p (pentet) dd (doublet of doublet), m (multiplet) and br. s (broad singlet). GC-yields were calculated using isooctane as internal standard. All measurements were carried out at room temperature unless otherwise stated. Electron impact (EI) mass spectra were recorded on AMD 402 mass spectrometer (70 eV). High resolution mass spectra (HRMS) were recorded on Agilent 6210. The data are given as mass units per charge (m/z). Gas chromatography analysis was performed on an Agilent HP-7890A instrument with a FID detector and HP-5 capillary column (polydimethylsiloxane with 5% phenyl groups, 30 m, 0.32 mm i.d., 0.25 μm film thickness) using argon as carrier gas. The products were isolated from the reaction mixture by column chromatography on silica gel 60, 0.063-0.2 mm, 70-230 mesh (Merck).

General Procedure

A 4 mL screw-cap vial was charged with Pd(TFA)2 (1.66 mg, 2 mol%), DPPP (4.1 mg, 4 mol%), DMC/MeOH (1.5/1.0 mL) and an oven-dried stirring bar. The vial was closed by Teflon septum and phenolic cap and connected with atmosphere with a needle. After benzyl alcohol (0.25 mmol) were injected by syringe, the vial was fixed in an alloy plate and put into Paar 4560 series autoclave (300 mL) under argon atmosphere. At room temperature, the autoclave is flushed with carbon monoxide for three times and 20 bar of carbon monoxide was charged. The autoclave was placed on a heating plate equipped with magnetic stirring and an aluminum block. The reaction is allowed to be heated under 135 oC for 24 hours. Afterwards, the autoclave is cooled to room temperature and the pressure was carefully released. After removal of solvent under reduced pressure, pure product was obtained by column chromatography on silica gel (eluent: pentane/ethyl acetate = 100:1).

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2018

Analytic Data of Products

Methyl 2-phenylacetateO

O1H NMR (300 MHz, Chloroform-d) δ 7.28 – 7.14 (m, 5H), 3.61 (s, 3H), 3.55 (s, 2H).13C NMR (75 MHz, CDCl3) δ 172.02, 134.01, 129.26, 128.60, 127.12, 52.04, 41.22.

Methyl 2-(o-tolyl)acetate

O

O

1H NMR (300 MHz, Chloroform-d) δ 7.19 (t, J = 1.9 Hz, 4H), 3.70 (s, 3H), 3.65 (s, 2H), 2.32 (s, 3H).13C NMR (75 MHz, CDCl3) δ 171.95, 136.84, 132.72, 130.35, 130.16, 127.42, 126.14, 52.02, 39.06, 19.59.

Methyl 2-(4-methoxyphenyl)acetate

O

OO

1H NMR (300 MHz, Chloroform-d) δ 7.23 – 7.09 (m, 2H), 6.86 (d, J = 8.6 Hz, 2H), 3.79 (d, J = 0.6 Hz, 3H), 3.68 (d, J = 0.6 Hz, 3H), 3.57 (s, 2H).13C NMR (75 MHz, CDCl3) δ 172.37, 158.70, 130.27, 126.04, 114.00, 55.25, 52.00, 40.28.


O

O

O

1H NMR (300 MHz, Chloroform-d) δ 7.23 – 7.14 (m, 1H), 7.10 (dd, J = 7.4, 1.7 Hz, 1H), 6.89 – 6.74 (m, 2H), 3.73 (s, 3H), 3.61 (s, 3H), 3.56 (s, 2H).13C NMR (75 MHz, CDCl3) δ 172.31, 157.51, 130.86, 128.57, 123.01, 120.51, 110.50, 55.46, 51.90, 35.76.

Methyl 2-(naphthalen-1-yl)acetate

O

O

1H NMR (300 MHz, Chloroform-d) δ 8.04 – 7.99 (m, 1H), 7.92 – 7.86 (m, 1H), 7.85 – 7.79 (m, 1H), 7.60 – 7.40 (m, 4H), 4.10 (s, 2H), 3.70 (s, 3H).

13C NMR (75 MHz, CDCl3) δ 172.07, 133.86, 132.14, 130.55, 128.78, 128.15, 128.06, 126.45, 125.84, 125.53, 124.99, 123.81, 52.20, 39.10.

Methyl 2-(2-benzylphenyl)acetate

O

O

1H NMR (300 MHz, Chloroform-d) δ 7.25 – 6.97 (m, 9H), 3.96 (s, 2H), 3.51 (d, J = 0.9 Hz, 5H).13C NMR (75 MHz, CDCl3) δ 171.93, 140.13, 139.27, 132.96, 130.91, 130.80, 128.81, 128.50, 127.63, 126.86, 126.16, 52.02, 39.15, 38.77.

Methyl 2-(3-(trifluoromethyl)phenyl)acetate

O

O

F3C

1H NMR (300 MHz, Chloroform-d) δ 7.56 – 7.41 (m, 4H), 3.71 (s, 3H), 3.69 (s, 2H).13C NMR (75 MHz, Chloroform-d) δ 171.24 , 134.83 , 133.35 – 132.13 (m), 130.93 (d, J = 32.3 Hz), 129.01 , 126.31 – 125.52 (m), 124.05 (q, J = 3.9 Hz), 52.21 , 40.79 .

Methyl 2-(2-((3-methoxyphenyl)dimethylsilyl)phenyl)acetate

Si O

OO

1H NMR (300 MHz, Chloroform-d) δ 7.60 (ddd, J = 7.3, 1.9, 0.8 Hz, 1H), 7.49 – 7.37 (m, 1H), 7.36 – 7.26 (m, 3H), 7.09 (dt, J = 7.2, 1.0 Hz, 1H), 7.05 (ddd, J = 2.7, 1.0, 0.5 Hz, 1H), 6.94 (ddd, J = 8.2, 2.7, 1.0 Hz, 1H), 3.80 (s, 3H), 3.63 (s, 2H), 3.59 (s, 3H).13C NMR (75 MHz, CDCl3) δ 173.10, 160.15, 141.29, 141.00, 137.91, 136.78, 131.51, 130.88, 130.26, 127.54, 127.40, 120.61, 115.47, 56.13, 52.86, 42.35, 0.00.

Methyl 2-(2-(trifluoromethyl)phenyl)acetate

OO

CF3

1H NMR (300 MHz, Chloroform-d) δ 7.69 – 7.63 (m, 1H), 7.56 – 7.48 (m, 1H), 7.43 – 7.35 (m, 2H), 3.84 (p, J = 1.3 Hz, 2H), 3.71 (s, 3H).13C NMR (75 MHz, Chloroform-d) δ 171.13 , 132.51 , 131.92 (d, J = 1.4 Hz), 128.98 (d, J = 30.1 Hz), 127.41 , 126.09 (q, J = 5.5 Hz), 122.47 , 52.19 , 38.04 (d, J = 2.0 Hz).


OO

O

1H NMR (300 MHz, Chloroform-d) δ 7.24 – 7.07 (m, 1H), 6.89 – 6.63 (m, 3H), 3.72 (s, 3H), 3.62 (s, 3H), 3.52 (s, 2H).13C NMR (75 MHz, CDCl3) δ 171.89, 159.73, 135.40, 129.56, 121.60, 114.92, 112.65, 55.20, 52.06, 41.25.

Methyl 2-(4-((trifluoromethyl)thio)phenyl)acetate

O

OS

F3C

1H NMR (300 MHz, Chloroform-d) δ 7.70 – 7.54 (m, 2H), 7.39 – 7.30 (m, 2H), 3.71 (s, 3H), 3.66 (s, 2H).13C NMR (75 MHz, CDCl3) δ 171.19, 137.11, 136.51, 131.60, 130.46, 127.52, 123.14, 123.11, 52.21, 40.77.

Methyl 2-(4-fluorophenyl)acetate

O

OF

1H NMR (300 MHz, Chloroform-d) δ 7.21 – 7.12 (m, 2H), 7.00 – 6.87 (m, 2H), 3.62 (s, 3H), 3.52 (d, J = 0.7 Hz, 2H).13C NMR (75 MHz, Chloroform-d) δ 171.87 , 162.04 (d, J = 245.4 Hz), 130.81 (d, J = 8.1 Hz), 129.67 (d, J = 3.3 Hz), 115.42 (d, J = 21.5 Hz), 52.08 , 40.28

Methyl 2-(benzo[d][1,3]dioxol-5-yl)acetateO

O

O

O

1H NMR (300 MHz, Chloroform-d) δ 6.84 – 6.64 (m, 3H), 5.93 (s, 2H), 3.69 (s, 3H), 3.53 (t, J = 0.5 Hz, 2H).13C NMR (75 MHz, CDCl3) δ 172.09, 147.77, 146.73, 127.54, 122.38, 109.71, 108.29, 101.03, 52.04, 40.78.

2-(Thiophen-2-yl)ethyl 2-phenylacetateO

O

S

1H NMR (300 MHz, Chloroform-d) δ 7.30 – 7.10 (m, 6H), 6.91 – 6.70 (m, 2H), 4.23 (t, J = 6.8 Hz, 2H), 3.54 (s, 2H), 2.94 – 2.75 (m, 2H).13C NMR (75 MHz, CDCl3) δ 171.46, 137.91, 133.99, 129.28, 128.59, 128.24, 127.09, 125.54, 121.63, 64.69, 41.48, 29.53.

Ethyl 2-phenylacetate

O

O

1H NMR (300 MHz, Chloroform-d) δ 7.32 – 7.08 (m, 5H), 4.08 (q, J = 7.1 Hz, 2H), 3.54 (s, 2H), 1.18 (t, J = 7.1 Hz, 3H).13C NMR (75 MHz, CDCl3) δ 171.61, 134.17, 129.24, 128.54, 127.03, 60.85, 41.45, 14.18.

01234567891011121314f1 (ppm)

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171110.f314.10.fidYahui Li L-69PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1711 14

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5.07

O

O

C H 3

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260171110.f314.11.fidYahui Li L-69C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1711 14 41

.22

52.0

4

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1212

8.60

129.

2613

4.01

172.

02

O

O

C H 3

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4500170403.f317.10.fidYahui Li L-50-1PROTON CDCl3 {C:\Bruker\TopSpin3.2PL6} 1704 17

3.00

2.01

2.96

4.03

C H 3

O

O

C H 3

-60-50-40-30-20-100102030405060708090100110120130140150160170180190200210220230240250260f1 (ppm)

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170403.f317.11.fidYahui Li L-50-1C13CPD CDCl3 {C:\Bruker\TopSpin3.2PL6} 1704 17 19

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52.0

2

126.

1412

7.42

130.

1613

0.35

132.

7213

6.84

171.

95

C H 3

O

O

C H 3

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2.00

2.95

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O

O

C H 3

OCH 3

-60-50-40-30-20-100102030405060708090100110120130140150160170180190200210220230240250260f1 (ppm)

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O

O

C H 3

OCH 3

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O

O

C H 3

OCH 3

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O

O

C H 3

OCH 3

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13000170404.309.10.fidYahui Li L-50-6Au1H CDCl3 /opt/topspin 1704 9

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1.99

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0.90

0.93

0.92

O

O

C H 3

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30000170404.309.11.fidYahui Li L-50-6Au13C CDCl3 /opt/topspin 1704 9 39

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8112

4.99

125.

5312

5.84

126.

4512

8.06

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133.

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172.

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O

O

C H 3

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24000170404.310.10.fidYahui Li L-50-7Au1H CDCl3 /opt/topspin 1704 10

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9.00

O

O

C H 3

0102030405060708090100110120130140150160170180190200210f1 (ppm)

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130000170404.310.11.fidYahui Li L-50-7Au13C CDCl3 /opt/topspin 1704 10 38

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39.1

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1612

6.86

127.

6312

8.50

128.

8113

0.80

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9113

2.96

139.

2714

0.13

171.

93

O

O

C H 3

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

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170428.f333.10.fidYahui Li L-93-1PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1704 33

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4.06

O

O

C H 3

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FF

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CH 3 C H 3

OC H 3

OOC H 3

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450170428.f334.11.fidYahui Li L-93-2C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1704 34 0.

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Si

CH 3 C H 3

OC H 3

OOC H 3

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85000170919.f341.10.fidLi/ L-183-3PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1709 41

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O

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supporting information general remarks were collected · pdf filewere collected from the...

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