the royal society of chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1...
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1
Electronic Supporting Information
Selective C-H Bond Electro-oxidation of Benzylic Acetates and Alcohols to
Benzaldehydes
Mateus R. Baroneab and Alan M. Jonesc*
a Department of Chemical Engineering, University of Sao Paulo, Brazil
b Division of Chemistry and Environmental Science, Manchester Metropolitan University, M1
5GD, UK
c School of Pharmacy, University of Birmingham, Edgbaston, B15 2TT, UK
Corresponding author: Dr Alan M. Jones, email [email protected] phone +44(0)1214-
147288, web: www.jonesgroupresearch.wordpress.com
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017
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2
Contents
S1. Copies of 1H and 13C NMR spectra pages 3-15
S2. Selected cyclic voltammetry data pages 16-20
S3. References page 21
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3
S1 Copies of 1H and 13C NMR spectra
1H NMR spectra of 1a (400 MHz, CDCl3)
MB-ester-1_Proton_ft-1-1.esp
Chemical Shift (ppm)12 11 10 9 8 7 6 5 4 3 2 1 0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
2.9
8
2.0
1
5.0
0
M01(m)
M02(m)
M03(m)
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
57
.35
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
O
O
13C NMR spectra of 1a (100 MHz, CDCl3)
MBE1_Carbon_ft-1-1.esp
Chemical Shift (ppm)220 200 180 160 140 120 100 80 60 40 20
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
M06(s)
M05(s)
M04(s)
M03(s)
M02(s)
M01(s)
21.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
32
1.1
3
66.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
16
6.4
1
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.35
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
128
.66
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
135
.99
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
171
.03
O
O
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4
1H NMR spectra 1b (400 MHz, CDCl3)
MB-ester-2_Proton_ft-1-1.jdf
Chemical Shift (ppm)12 11 10 9 8 7 6 5 4 3 2 1 0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
3.0
7
3.0
5
2.0
0
2.0
2
2.0
0
M04(m)
M02(m)
M05(m)
M03(m)
M01(s)
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
5.0
75
.07
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
O
O
13C NMR spectra 1b (100 MHz, CDCl3)
MBE2_Carbon_ft-1-1.esp
Chemical Shift (ppm)220 200 180 160 140 120 100 80 60 40 20
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
M08(s)
M07(s)
M05(s)
M06(s)
M04(s)
M03(s)
M02(s)
M01(s)
21.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
52
1.1
5
21.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
92
1.2
966.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
76
6.3
7
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
128
.54
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
129
.33
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
132
.98
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
138
.23
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
171
.07
O
O
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5
1H NMR spectra 1c (400 MHz, CDCl3)
MB-ester-3_Proton_ft-1-1.jdf
Chemical Shift (ppm)12 11 10 9 8 7 6 5 4 3 2 1 0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
3.0
0
2.0
6
2.0
0
2.0
0
M04(m)
M03(m)
M02(s)
M01(m)
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
5.0
55
.05
O
O
Cl
13C NMR spectra 1c (100 MHz, CDCl3)
MBE3_Carbon_ft-1-1.esp
Chemical Shift (ppm)220 200 180 160 140 120 100 80 60 40 20
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
M07(s)
M05(s)
M01(s)
M06(s)
M04(s)
M03(s)
M02(s)
21.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
72
1.0
765.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
56
5.5
5128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
128
.84
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
129
.73
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
134
.50
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
170
.88
O
O
Cl
![Page 6: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/6.jpg)
6
1H NMR spectra 1e (400 MHz, CDCl3)
MB-ester-4_Proton_ft-1-1.jdf
Chemical Shift (ppm)12 11 10 9 8 7 6 5 4 3 2 1 0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
3.0
0
2.0
3
2.0
4
4.9
2
M01(m)
M04(m) M02(m)
M03(m)
O
O
![Page 7: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/7.jpg)
7
1H NMR spectra of 2a (300 MHz, CD3OD)
![Page 8: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/8.jpg)
8
1H NMR spectra of 2b (300 MHz, CD3OD)
![Page 9: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/9.jpg)
9
1H NMR spectra of 2c (300 MHz, CDCl3)
![Page 10: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/10.jpg)
10
1H NMR spectra of 2f (300 MHz, CDCl3)
![Page 11: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/11.jpg)
11
1H NMR spectra of 2g (300 MHz, CDCl3)
![Page 12: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/12.jpg)
12
1H NMR spectra of 2h (400 MHz, CDCl3)
![Page 13: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/13.jpg)
13
1H NMR spectra of 2i (300 MHz, CDCl3)
![Page 14: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/14.jpg)
14
1H NMR spectra of 2j (300 MHz, CDCl3)
![Page 15: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/15.jpg)
15
1H NMR spectra of 2k (300 MHz, CDCl3)
![Page 16: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/16.jpg)
16
S2 Selected Cyclic Voltammetry data
Analyte: 1a
Scan rate: 10 mV/s - 250 mV/s
Electrolyte: TBAP
General Procedure C used, further details and experimental set-up are shown in ref. S1.
Voltage (V)
0
0.001
0.002
0.003
0.004
0.005
0.006
0 0.5 1 1.5 2 2.5
Blank
10mV/s
25mV/s
50mV/s
100mV/s
250mV/s
Cu
rren
t (A
)
![Page 17: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/17.jpg)
17
Analyte: 1b
Scan rate: 10 mV/s - 250 mV/s
Electrolyte: TBAP
General Procedure followed: C
Voltage (V)
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0 0.5 1 1.5 2 2.5
Blank
10 mV/s
25 mV/s
50 mV/s
100 mV/s
250 mV/s
Cu
rren
t (A
)
![Page 18: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/18.jpg)
18
Analyte: 1c
Scan rate: 10 mV/s - 250 mV/s
Electrolyte: TBAP
General Procedure followed: C
Voltage (V)
0
0.001
0.002
0.003
0.004
0.005
0.006
0 0.5 1 1.5 2 2.5
Blank
10 mV/s
25 mV/s
50 mV/s
100 mV/s
250 mV/s
50 mV/sCu
rren
t (A
)
![Page 19: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/19.jpg)
19
Analyte: 1e
Scan rate: 10 mV/s - 250 mV/s
Electrolyte: TBAP
General Procedure followed: C
Voltage (V)
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0 0.5 1 1.5 2 2.5
Blank
10mV/s
25mV/s
50mV/s
100mV/s
250mV/s
Cu
rren
t (A
)
![Page 20: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/20.jpg)
20
Analyte: 3a
Scan rate: 25 mV/s - 100 mV/s
Electrolyte: TBAP or LiClO4
General Procedure followed: C
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0 0.5 1 1.5 2 2.5 3
Cu
rren
t (A
)
Voltage (V)
LiClO4 25mV/s
LiClO4 100mV/s
TBAP 25mV/s
TBAP 100 mV/s
![Page 21: The Royal Society of Chemistry › suppdata › c7 › ob › c7ob02300f › c7ob02300f1.pdf · 1 Electronic Supporting Information Selective C-H Bond Electro-oxidation of Benzylic](https://reader033.vdocuments.site/reader033/viewer/2022053013/5f1086567e708231d4498983/html5/thumbnails/21.jpg)
21
S3 References
[S1] P. Alfonso-Súarez, A. V. Kolliopoulos, J. P. Smith, C. E. Banks, A. M. Jones, Tetrahedron
Lett., 2015, 56, 6863.