methyl glycosides are identified as glycosyl donors for ... · stable methyl glycosides are...
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Supporting Information for
Methyl Glycosides Are Identified as Glycosyl Donors for the Synthesis of Glycosides, Disaccharides and Oligosaccharides
Srinivasa Rao Vidadala and Srinivas Hotha*
Division of Organic Chemistry, Combi Chem – Bio Resource Center National Chemical Laboratory, Pune – 411 008, INDIA
Fax: (+) 91 20 2590 2624
Contents
Page Number
Abstract 2
General Experimental Techniques 2
General Experimental Procedure 2 1H, 13C and DEPT NMR Spectral Charts of Compounds 1, 2a, 2b, 2f, 2g, 2h, 3a, 3b, 4a, 5a, 5b, 5c, 5d, 5e, 5f, 5g, 5h, 5i, 5j, 6a, 6b, 6c, 6d, 7a, 7b, 7c, 8a, 8b, 8c, 9a, 9b, 10b, 11, 12
3-36
Mass Spectral Characterization Data 37
UPLC Chromatograms of Crude Reaction Mixtures 38-53
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Abstract
Stable methyl glycosides are identified as glycosyl donors in the presence of AuBr3 in acetonitrile. A panel of aglycones comprising aliphatic, alicyclic, steroidal and sugar alcohols are examined successfully for the glycosylation reaction. Methyl glycosides of di- and tri- saccharides are converted to corresponding tri- and tetra- saccharides exploiting salient features of our novel activation protocol.
General Experimental Techniques and Apparatus Unless otherwise noted, materials were obtained from commercial suppliers and were used without further
purification. Unless otherwise reported all reactions were performed under argon atmosphere. Removal of solvent in vacuo refers to distillation using a rotary evaporator attached to an efficient vacuum pump. Products obtained as solids or syrups were dried under high vacuum. AuCl3 was purchased from Aldrich. Analytical thin-layer chromatography was performed on pre-coated silica plates (F254, 0.25 mm thickness); compounds were visualized by UV light or by staining with anisaldehyde spray. 1H, 13C NMR spectra were recorded on 200 MHz for 1H and 50 MHz for 13C NMR or 300 MHz for 1H and 75 MHz for 13C NMR or 500 MHz for 1H and 125 MHz for 13C NMR spectrometers. LC-MS data was recorded on UPLC coupled Mass Spectrometer (Waters). Chemical shifts (δH) are quoted in ppm and are referenced to tetramethylsilane (internal).
General Procedure for AuBr3 mediated Glycosylation
To a solution of glycosyl donor (0.1 mmol) and aglycone (0.12 mmol) in anhydrous acetonitrile (4 ml) was added 10
mol% of AuBr3 under argon atmosphere at room temperature. The resulting mixture was heated to 70oC and stirred till the completion of the reaction as judged by TLC analysis (Table 1 of manuscript). The reaction mixture was concentrated in vacuo to obtain a crude residue which was purified by conventional silica gel column chromatography using ethyl acetate-petroleum ether as mobile phase.
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Spectral Charts
1H NMR (200.13 MHz, CDCl3) of compound 1
9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
21.00 4.88 3.341.451.04 0.65
2.38
2.39
2.40
3.69
3.75
3.76
3.833.83
3.84
4.01
4.19
4.20
4.26
4.474.
524.
564.
60
4.74
4.85
5.08
5.09
7.137.
14
7.167.
187.
247.
28
7.31
7.32
7.33
7.36
7.37
7.38
7.41
13C NMR (125.76 MHz, CDCl3) of compound 1
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
54.1
8
69.1
672
.14
72.3
073
.45
74.7
975
.17
76.4
377
.07
77.7
180
.05
96.4
7
127.
6212
8.35
138.
2413
8.45
138.
50
DEPT NMR (125.76 MHz, CDCl3) of compound 1
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.18
69.1672.14
72.2
9
72.7073.45
74.4
074
.78
75.18
80.0
5
96.4
7
127.
6312
8.35
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1H NMR (200.13 MHz, CDCl3) of compound 2a
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
15.44 6.92 4.610.96
3.35
3.53
3.56
4.01
4.05
4.55
4.574.664.
68
4.764.
86
4.96
5.02
7.227.22
7.28
7.29
7.32
7.34
7.36
7.37
13C NMR (125.76 MHz, CDCl3) of compound 2a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 00.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.2
4
61.8
5
70.7
9
73.4
6
75.0
8
75.7
976
.55
77.1
8
77.8
282
.01
98.2
3
127.
6812
8.03
128.
54
138.
24
138.
82
DEPT NMR (125.76 MHz, CDCl3) of compound 2a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.2
5
61.83
70.7
8
73.4875.1075.82
77.4
480
.02
82.0
1
98.2
2
127.
7112
7.95
128.
0512
8.56
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1H NMR (200.13 MHz, CDCl3) of compound 2b
10 9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
9.466.00 3.032.041.990.99 0.91
0.00
3.47
3.76
3.77
4.075.26
5.27
5.51
5.566.24
7.257.26
7.287.37
7.38
7.39
7.43
7.50
7.51
7.87
7.96
7.97
8.00
13C NMR (50.32 MHz, CDCl3) of compound 2b
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.6
4
61.0
869
.55
69.8
070
.14
72.0
676
.42
77.0
577
.69
97.1
5
128.
3012
8.52
129.
6412
9.91
133.
15
133.
70
165.
8216
6.39
DEPT NMR (50.32 MHz, CDCl3) of compound 2b
150 100 50 0
0.0
0.5
1.0
55.6
7
61.08
69.5
669
.80
72.0
8
97.1
5
128.
3512
8.46
129.
6812
9.95
133.
4313
3.76
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1H NMR (200.13 MHz, CDCl3) of compound 2f
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
12.044.28 3.63 3.002.15 1.780.92
3.36
3.47
3.83
3.98
4.00
4.62
4.63
5.145.
15
5.27
5.29
5.817.
227.
247.
267.
267.
297.
307.
337.
347.
357.
447.
457.
487.
917.
947.
957.
98
13C NMR (50.32 MHz, CDCl3) of compound 2f
150 100 50 00.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
0
69.4
770
.34
70.5
271
.72
73.7
874
.05
77.2
777
.9197.1
3
127.
7712
8.44
129.
9213
3.39
137.
97
166.
0816
7.29
DEPT NMR (50.32 MHz, CDCl3) of compound 2f
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
55.4
0
69.43
70.3
070
.51
71.7
2
73.78
74.0
2
97.1
1
127.
7812
8.45
129.
9213
3.41
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1H NMR (200.13 MHz, CDCl3) of compound 2g
10 9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
11.147.19 3.523.323.23 1.701.00
TMS
0.00
2.46
3.49
3.51
3.82
3.82
3.84
4.09
4.10
5.005.01
5.675.685.68
5.695.85
5.95
5.97
6.007.
21
7.25
7.38
7.42
7.48
7.49
7.52
7.58
7.61
7.96
8.008.
09
8.13
13C NMR (50.32 MHz, CDCl3) of compound 2g
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.5
1
61.4
367.3
069
.69
70.5
870
.89
76.4
677
.09
77.7
3
98.7
9
128.
3112
8.54
129.
95
133.
5713
3.68
165.
5016
5.58
166.
49
DEPT NMR (50.32 MHz, CDCl3) of compound 2g
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
55.5
2
61.41
67.2
969
.67
70.5
770
.87
98.7
7
128.
32128.
5512
9.73
129.
9513
3.22
133.
60
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1H NMR (200.13 MHz, CDCl3) of compound 2h
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
10.486.75 3.322.11 1.021.00 0.95
TMS
0.00
2.79
3.56
3.79
3.84
3.86
4.754.79
5.475.
485.
525.
535.
575.
925.97
6.027.22
7.25
7.36
7.37
7.40
7.41
7.50
7.52
7.82
7.93
7.94
7.95
7.98
7.99
13C NMR (50.32 MHz, CDCl3) of compound 2h
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
57.2
4
61.3
569
.61
71.8
772
.87
74.6
876
.51
77.1
577
.78
102.
12
128.
3512
9.85
129.
9613
3.28
133.
73
165.
2116
5.90
166.
09
DEPT NMR (50.32 MHz, CDCl3) of compound 2h
150 100 50 0
0.0
0.5
1.0
57.2
7
61.33
69.6
171
.86
72.8
574
.67
102.
11
128.
3512
8.40
129.
7612
9.86
133.
3113
3.75
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1H NMR (200.13 MHz, CDCl3) of compound 3a
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
45.13 20.28 12.81 3.00
0.00
1.26
3.30
3.643.65
3.683.80
3.82
3.97
4.46
4.58
4.61
4.70
4.83
4.96
5.017.
127.147.16
7.19
7.23
7.27
7.32
7.34
13C NMR (50.32 MHz, CDCl3) of compound 3a
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
29.7
6
55.1
5
69.1
769.8
872
.06
73.3
376
.50
77.1
477
.77
80.0
682
.20
97.8
998
.33
127.
48
127.
7412
7.92
128.
0812
8.30
128.
4312
8.56
138.
21138.
4213
8.72
DEPT NMR (50.32 MHz, CDCl3) of compound 3a
150 100 50 0
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
29.77
55.1
6
65.8669.13
69.8
6
72.0672.5173.33
74.6
574
.89
75.0175.1075.89
77.6
679
.60
80.0
382
.20
97.8
898
.31
127.
7612
7.83
128.
1012
8.32
128.
4512
8.57
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1H NMR (200.13 MHz, CDCl3) of compound 3b
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
32.906.03 5.785.542.132.091.00 1.00
0.00
1.26
1.70
3.38
3.62
3.66
3.87
3.88
3.91
4.414.
474.
484.69
4.90
4.915.17
5.19
5.265.
566.
066.11
7.147.
167.18
7.21
7.25
7.27
7.28
7.34
7.37
7.38
7.41
7.87
7.88
7.96
8.00
13C NMR (50.32 MHz, CDCl3) of compound 3b
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.5
6
66.1
869
.0769.8
670
.57
72.1
173
.25
76.4
377
.06
77.7
079
.91
96.9
798
.26
127.
4112
7.55
127.
71128.
3312
8.44
129.
9713
3.08
138.
5013
8.64
165.
1216
5.87
DEPT NMR (50 MHz, CDCl3) of compound 3b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.5
7
66.17
68.1
1
69.03
69.8
470
.54
72.10
72.1
4
72.6173.25
74.7
6
75.05
79.9
0
96.9
598
.2412
7.43
127.
5512
7.73
128.
27128.
3512
9.94
133.
1013
3.30
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1H NMR (200.13 MHz, CDCl3) of compound 4a
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
19.80 4.72 2.571.981.141.00
0.00
3.34
3.35
3.583.58
3.68
3.703.89
3.89
3.93
4.41
4.42
4.54
4.554.57
4.59
4.605.
46
7.217.22
7.24
7.25
7.32
7.33
7.37
7.42
13C NMR (50.32 MHz, CDCl3) of compound 4a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
65.4
871
.24
71.8
472
.09
74.4
576
.27
76.4
877
.11
77.7
4
100.
67
127.
7912
7.9012
8.49
128.
6412
9.9813
7.94
DEPT NMR (50.32 MHz, CDCl3) of compound 4a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
65.4471.2371.8372.05
74.4
276
.00
76.7
5
100.
64
127.
7412
7.81
127.
9112
8.51
128.
6612
9.99
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1H NMR (200.13 MHz, CDCl3) of compound 5a
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
20.60 9.36 3.97 3.00
3.30
3.76
3.92
4.48
4.50
4.53
4.56
4.58
4.72
4.78
4.86
4.92
7.18
7.18
7.23
7.25
7.28
7.32
7.35
13C NMR (50.32 MHz, CDCl3) of compound 5a
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.7
7
69.3
572.1
572
.65
73.4
174
.97
76.4
377.0
777
.70
80.2
7
99.0
1127.
5012
7.64
128.
32
138.
3913
8.44138.
56
DEPT NMR (50.32 MHz, CDCl3) of compound 5a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.7
8
69.32
71.7
0
72.1472.6473.40
74.5
774
.94
75.1280
.25
98.9
9
127.
6412
8.34
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1H NMR (200.13 MHz, CDCl3) of compound 5b
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
22.31 5.32 5.28 3.002.09 1.19
0.00
1.11
1.14
1.18
1.76
1.77
3.383.
433.
463.673.71
3.72
3.76
3.79
3.95
4.00
4.47
4.51
4.52
4.57
4.62
4.74
4.90
4.91
7.127.
137.
157.17
7.21
7.24
7.25
7.27
7.33
7.36
7.37
7.38
7.40
13C NMR (50.32 MHz, CDCl3) of compound 5b
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
15.0
5
62.9
871
.79
72.1
872
.63
73.4
375
.11
76.5
077
.13
77.7
680
.46
97.6
8
127.
6312
8.38
138.
5013
8.69
DEPT NMR (50.32 MHz, CDCl3) of compound 5b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
15.0
5
62.98
69.36
71.7
6
72.1772.6273.43
74.8
375
.08
75.2680
.44
97.6
7127.
5412
7.63
128.
39
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1H NMR (200.13 MHz, CDCl3) of compound 5c
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
21.53 7.24 6.002.971.09
0.00
1.04
1.07
1.14
1.17
3.69
3.74
3.75
3.78
3.83
3.93
4.01
4.52
4.56
4.63
4.73
4.75
4.82
4.96
4.97
7.127.
147.
157.17
7.24
7.26
7.27
7.33
7.34
7.36
7.37
7.38
7.41
13C NMR (100.61 MHz, CDCl3) of compound 5c
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
21.2
723
.27
68.9
371
.78
72.1
772
.67
73.3
775
.24
76.4
577
.08
77.7
280
.43
95.8
7127.
5212
7.61
128.
36
138.
5013
8.72
DEPT NMR (100.61 MHz, CDCl3) of compound 5c
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
21.2
623
.28
68.9
2
69.34
71.7
4
72.1772.6773.37
75.1
8
75.26
80.4
2
95.8
4
127.
4912
7.62
128.
38
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
15
1H NMR (200.13 MHz, CDCl3) of compound 5d
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
25.51 9.27 6.171.04
0.003.
743.
753.763.783.
81
3.98
4.034.
414.
47
4.61
4.71
4.854.
974.
98
7.147.
167.18
7.21
7.247.
257.
287.
317.
337.
34
13C NMR (50.32 MHz, CDCl3) of compound 5d
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
69.0
272
.27
72.6
573
.46
75.0
775
.25
76.5
177
.14
77.7
880
.32
97.2
6
127.
6712
7.74
127.
9212
8.40
128.
4813
7.42
138.
3513
8.53
138.
61
DEPT NMR (50.32 MHz, CDCl3) of compound 5d
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
69.02
72.1
4
72.2772.6573.46
74.7
175
.04
75.27
80.3
1
97.2
5127.
6312
7.74
127.
9312
8.40
128.
48
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
16
1H NMR (200.13 MHz, CDCl3) of compound 5e
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
47.1421.95 8.72 6.69 6.282.621.191.04
0.00
0.07
0.67
0.85
0.88
0.97
1.11
1.25
1.44
1.55
1.65
1.78
1.972.28
3.66
3.753.76
3.77
3.79
3.96
4.01
4.484.
524.
544.
63
4.73
4.74
4.855.02
5.03
5.287.147.
157.177.
187.
25
7.25
7.277.
307.
337.
347.
357.
377.
387.
40
13C NMR (50.32 MHz, CDCl3) of compound 5e
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
11.8
9
18.7
619
.37
21.0
822
.59
22.8
623
.86
28.0
5
31.9
135
.82
36.7
139
.5542.3
5
50.1
1
56.1
856
.79
69.4
072.1
572
.60
73.3
275
.29
76.4
277
.05
77.6
880
.40
95.8
0
121.
86127.
5012
7.60
128.
35
138.
4813
8.70
140.
64
DEPT NMR (50.32 MHz, CDCl3) of compound 5e
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
11.8
9
18.7
619
.37
21.08
22.6
122
.87
23.8627.63
28.0
6
28.2729.74
31.9
0
31.95
35.8
3
36.2237.01
39.5539.79
50.1
0
56.1
756
.79
69.3672.1472.5973.32
75.1
6
75.23
76.5
3
80.3
9
95.7
6
121.
87127.
4412
7.60
128.
36
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
17
1H NMR (200.13 MHz, CDCl3) of compound 5f
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
20.86 7.28 3.922.311.97 1.111.00
0.00
3.703.
743.
763.81
3.94
3.96
3.97
4.11
4.14
4.18
4.50
4.53
4.56
4.61
4.73
4.91
4.92
4.93
5.11
5.165.16
5.22
5.24
5.25
5.77
5.77
5.80
5.82
5.85
7.137.
147.
167.
187.
247.26
7.27
7.33
7.35
7.38
7.40
13C NMR (50.32 MHz, CDCl3) of compound 5f
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
67.8
872
.25
72.6
973
.44
75.0
575
.23
76.5
477
.17
77.8
180
.34
97.1
8117.
30127.
5512
7.71
128.
40
133.
88
138.
4313
8.57
DEPT NMR (50.32 MHz, CDCl3) of compound 5f
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
67.88
71.9
4
72.2472.6773.43
74.7
275
.02
75.26
80.3
2
97.1
6
117.32
127.
6412
7.72
128.
41
133.
87
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
18
1H NMR (200.13 MHz, CDCl3) of compound 5g
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
19.74 4.933.191.00 0.94
3.37
3.55
3.68
3.70
3.72
3.953.994.
434.
494.
624.
634.
764.
804.84
4.96
5.017.
117.13
7.14
7.247.
257.
287.
297.
327.
33
13C NMR (50.32 MHz, CDCl3) of compound 5g
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.2
2
68.5
770
.12
73.4
473
.53
75.7
976
.47
77.1
177
.74
82.1
9
98.2
6
127.
6312
7.73
127.
9512
8.41
128.
4913
7.99
138.
2313
8.33
138.
87
DEPT NMR (50.32 MHz, CDCl3) of compound 5g
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.2
3
68.51
70.0
9
73.4573.53
75.0975.82
77.7
079
.87
82.1
9
98.2
6
127.
6612
7.74
127.
9212
7.97
128.
42
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
19
1H NMR (200.13 MHz, CDCl3) of compound 5h
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
22.33 2.932.82 1.00
3.45
3.483.49
3.54
3.56
3.72
3.734.
294.
334.49
4.55
4.58
4.68
4.81
4.91
4.96
7.127.
137.157.
177.
237.
247.
267.
287.
297.
327.
357.
367.
37
13C NMR (50.32 MHz, CDCl3) of compound 5h
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 00.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
57.2
7
69.0
873
.66
74.9
375
.04
75.8
678.0
482
.51
84.8
4
104.
90
127.
8012
7.98
128.
56
138.
3313
8.36
138.
82
DEPT NMR (50.32 MHz, CDCl3) of compound 5h
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.05
0.00
0.05
0.10
0.15
0.20
0.25 57.2
8
69.0573.6674.94
75.0
2
75.2175.87
78.0
3
82.5
184
.8310
4.90
127.
8112
7.98
128.
1612
8.30
128.
56
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
20
1H NMR (200.13 MHz, CDCl3) of compound 5i
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
25.04 11.35 4.02 3.00
0.00
3.37
3.53
3.54
3.91
3.95
4.00
4.41
4.45
4.604.67
4.69
4.71
4.75
4.804.82
4.92
4.97
7.24
7.25
7.27
7.30
7.35
7.37
13C NMR (50.32 MHz, CDCl3) of compound 5i
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
0
69.1
473.3
473
.53
76.4
677
.10
77.7
379
.17
98.8
6
127.
5412
8.43
138.
0513
8.72
138.
89
DEPT NMR (50.32 MHz, CDCl3) of compound 5i
130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
55.4
0
65.37
69.13
69.2
873.3473.53
74.79
75.2
176
.50
79.1
6
98.8
5
127.
0112
7.55
128.
4312
8.60
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
21
1H NMR (200.13 MHz, CDCl3) of compound 5j
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
19.95 6.914.04 2.111.00
3.483.50
3.54
3.58
3.82
3.88
3.904.
264.
294.
414.
424.
644.
72
4.87
4.91
4.934.97
7.25
7.26
7.28
7.29
7.31
7.33
7.34
13C NMR (50.32 MHz, CDCl3) of compound 5j
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
57.1
3
68.9
573.0
973
.47
73.6
675
.2676.5
977
.23
77.8
679
.75
82.2
4
105.
10
127.
6412
8.38
128.
4813
8.03
138.
6213
8.76
138.
94
DEPT NMR (50.32 MHz, CDCl3) of compound 5j
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
57.1
4
68.9473.08
73.4
7
73.6674.5775.27
79.7
582
.24
105.
09
127.
6512
8.40
128.
48
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
22
1H NMR (200.13 MHz, CDCl3) of compound 6a
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
21.20 7.45 5.374.12 2.501.941.131.00
0.00
1.58
1.61
1.65
1.682.00
2.03
2.07
2.10
2.113.
333.
353.
38
3.62
3.65
3.70
3.75
3.77
3.78
3.92
3.93
3.95
3.99
4.51
4.53
4.57
4.63
4.73
4.85
4.91
4.92
4.97
5.02
5.03
5.705.75
5.79
5.84
7.137.
14
7.167.
187.
227.
247.
267.
277.
347.
357.
367.
387.
40
13C NMR (50.32 MHz, CDCl3) of compound 6a
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
28.6
930
.35
66.9
971
.9372.2
572
.66
73.4
276
.52
77.1
577
.79
80.3
5
97.9
9
114.
97
127.
6412
7.74
127.
8812
8.39
138.
1113
8.50
138.
65
DEPT NMR (50.32 MHz, CDCl3) of compound 6a
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
28.6830.36
66.99
71.9
0
72.2572.6573.42
74.8
975
.07
75.24
80.3
4
97.9
8
114.97
127.
6512
7.74
127.
8412
8.11
128.
40
138.
11
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
23
1H NMR (200.13 MHz, CDCl3) of compound 6b
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
20.00 10.586.78 5.59 3.60 2.941.96 1.951.000.93
0.00
0.620.
65
0.800.
800.83
0.84
0.87
0.90
1.01
1.04
1.25
1.521.57
1.68
1.74
1.77
2.11
2.17
3.183.
233.
263.
293.
31
3.67
3.69
3.74
3.75
3.89
3.93
3.97
4.47
4.49
4.52
4.55
4.624.63
4.70
4.87
4.92
7.157.
167.
187.
19
7.247.
267.307.
307.
347.
367.
377.
38
13C NMR (50.32 MHz, CDCl3) of compound 6b
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Chlorof orm-d
16.2
5
20.9
9
22.1
3
23.2
1
25.7
1
31.5
7
34.2
4
42.8
2
48.6
3
69.4
872.2
2
72.3
6
73.2
6
75.1
2
75.2
476
.36
77.0
0
77.6
380
.06
81.0
6
99.8
3127.
35
127.
51127.
66
127.
75
127.
9712
8.29
138.
22
138.
53
DEPT NMR (50.32 MHz, CDCl3) of compound 6b
140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
16.2
4
21.0
022
.14
23.20
25.7
0
31.5
6
34.24
42.82
48.6
3
69.45
71.7
472.2372.3673.26
74.3
9
75.14
75.2
280
.06
81.0
5
99.8
3
127.
37
127.
7612
7.98
128.
0612
8.20
128.
30
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
24
1H NMR (200.13 MHz, CDCl3) of compound 6c
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
45.59 14.7112.136.11 3.38 3.002.592.20 1.10
-0.0
80.
00
3.34
3.75
3.79
4.11
4.32
4.36
4.37
4.394.
454.
484.
544.
554.
715.
075.08
5.875.92
5.95
6.92
6.93
7.047.
057.
067.
077.
097.
167.
177.
197.
197.
237.
277.
317.
417.
437.
847.857.
897.
907.
94
13C NMR (50.32 MHz, CDCl3) of compound 6c
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
5
71.5
972
.09
72.5
572
.9873
.44
76.4
577
.08
77.7
279
.73
96.8
2
100.
53
127.
1712
7.58
127.
7812
8.30
129.
7912
9.92
138.
3313
8.37
138.
56
165.
5916
5.93
DEPT NMR (50.32 MHz, CDCl3) of compound 6c
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
6
68.8669.37
69.8
8
71.57
72.0
8
72.54
72.9
573
.10
73.4074
.46
74.99
75.7
776
.73
79.7
1
96.8
0
100.
53
127.
1812
7.58
127.
7912
8.32
128.
4312
9.93
133.
3313
3.57
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
25
1H NMR (200.13 MHz, CDCl3) of compound 6d
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
30.24 7.196.11 5.092.882.00 1.11
0.00
1.26
3.43
3.693.71
3.73
3.93
3.97
4.37
4.43
4.62
4.814.
944.
965.
625.
635.
865.
885.
92
7.137.
157.17
7.21
7.23
7.24
7.26
7.30
7.31
7.40
7.44
7.49
7.80
7.848.
068.
098.
10
13C NMR (125.76 MHz, CDCl3) of compound 6d
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.45
69.13
69.9
9
70.65
71.8
6
72.54
73.2
576
.81
77.0
6
77.3
280
.17
98.16
98.51
127.5412
8.26
129.86
133.53
138.47
138.
65
165.41
DEPT NMR (125.76 MHz, CDCl3) of compound 6d
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
6
66.78
67.9
2
68.99
69.1
269
.99
70.6
5
71.85
71.9
4
72.5373.25
74.8
1
75.05
80.1
7
98.1
698
.50
127.
5512
8.26
129.
87
133.
53
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
26
1H NMR (200.13 MHz, CDCl3) of compound 7a
8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
33.36 11.03 9.877.45 3.442.821.141.00
0.00
3.38
3.43
3.45
3.563.
613.
634.
404.52
4.66
4.75
4.80
4.90
4.95
5.20
5.22
5.24
5.26
5.54
6.15
6.19
6.24
7.117.
137.15
7.24
7.26
7.28
7.32
7.36
7.40
7.47
7.50
7.96
8.00
13C NMR (50.32 MHz, CDCl3) of compound 7a
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.63
66.7168
.62
72.30
73.1573.45
76.46
77.10
77.74
81.79
82.40
84.60
96.80
97.28
104.05
127.54
127.68
127.98
128.30
128.45
129.98
133.38
137.98
138.45
138.63
138.93
165.29
165.88
DEPT NMR (50.32 MHz, CDCl3) of compound 7a
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.00
0.05
0.10
0.15
0.20
0.25
55.5
655
.64
66.6968.27
68.6
069
.66
70.2
570.6
572
.30
73.1873.45
73.8
7
74.8475.60
77.5
8
82.4
084
.59
96.7
797
.27
104.
04
127.
58
127.
7012
8.00
128.
0412
8.32
128.
46
129.
9813
3.41
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
27
1H NMR (500.13 MHz, CDCl3) of compound 7b
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
27.24 10.54 7.842.03 1.87 1.30
3.39
3.403.
453.
473.
543.
583.
683.
70
4.014.
03
4.05
4.23
4.37
4.40
4.51
4.55
4.57
4.58
4.794.
79
4.935.
00
5.00
5.02
5.02
5.05
5.715.72
5.73
5.85
5.92
5.93
5.94
5.95
6.00
6.02
7.187.19
7.237.25
7.28
7.29
7.297.
317.
387.
467.
477.
577.
587.
867.888.
00
8.02
8.138.
13
8.14
8.15
8.16
8.17
13C NMR (125.76 MHz, CDCl3) of compound 7b
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.5
1
62.8
667
.30
67.4
668
.27
69.6
070
.26
73.3
776
.85
77.1
077
.36
77.6
2
81.8
884
.53
97.3
398
.54
104.
17
104.58
127.
7012
7.92
128.
36
129.
7712
9.97
133.
45
138.
4113
8.62
165.
52
DEPT NMR (50.32 MHz, CDCl3) of compound 7b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
55.4
455
.52
62.85
66.9
7
67.28
67.4
4
68.24
68.70
69.5
970
.25
70.6
0
73.0873.36
74.8475.57
75.75
77.6
079
.98
81.8
784
.52
97.3
398
.53
98.6
6
104.
17
127.
5512
7.70
127.
9412
8.37
128.
4012
9.77
129.
9113
3.24
133.
4613
3.64
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
28
1H NMR (200.13 MHz, CDCl3) of compound 7c
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
34.65 12.276.59 5.964.342.141.00
-0.0
80.
00
3.25
3.30
3.36
3.56
3.58
4.33
4.36
4.384.
494.
554.
574.65
4.71
4.82
4.875.325.
365.
37
5.41
5.79
5.80
7.017.
037.
077.
097.
117.13
7.147.
157.
167.17
7.197.
227.
237.
277.
317.
357.
457.
707.847.
857.
867.
887.88
7.89
13C NMR (50.32 MHz, CDCl3) of compound 7c
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
-0.0
1
56.1
8
65.3
967
.26
68.9
772.2
475
.39
76.0
376
.66
80.8
583
.5395
.75100.
7810
2.92
126.
4112
6.50
126.
8812
7.30
127.
3812
8.79
128.
8513
2.14
136.
87137.
5213
7.81
164.
1616
4.77
DEPT NMR (50.32 MHz, CDCl3) of compound 7c
150 100 50 0
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.00
56.2
1
67.22
68.9
770
.84
72.2672.3273.6273.7273.9474.5874.65
76.4
878
.87
80.8
683
.52
95.7
4100.
7810
2.92
126.
42
126.
5012
6.90
127.
0512
7.24
127.
3212
8.69
128.
8113
2.16
132.
44
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
29
1H NMR (200.13 MHz, CDCl3) of compound 8a
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
30.306.31 3.803.50 3.212.031.00
0.00
3.34
3.35
3.41
3.50
3.94
4.00
4.03
4.33
4.36
4.70
4.75
4.79
4.815.17
5.19
5.20
5.24
5.546.13
7.19
7.23
7.26
7.29
7.30
7.32
7.33
7.37
7.40
7.50
7.88
7.88
7.917.96
7.97
8.00
13C NMR (50.32 MHz, CDCl3) of compound 8a
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.4
6
68.7
569
.62
70.7
572.2
373
.21
73.2
876
.47
77.1
177
.74
78.5
979
.68
82.0
7
96.7
196.8
297
.91
104.
29
127.
5812
8.27
128.
4512
9.98
133.
38
137.
9113
8.77
138.
81
165.
3816
5.86
DEPT NMR (50.32 MHz, CDCl3) of compound 8a
150 100 50 0
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
29.76
55.4
6
66.61
68.4
9
68.73
69.3
069
.58
70.7
372.2
2
72.9373.27
74.81
75.0
876
.45
78.5
779
.69
82.0
396.7
997
.89
104.
26
127.
5812
8.30
128.
4612
9.98
133.
40
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
30
1H NMR (200.13 MHz, CDCl3) of compound 8b
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
30.62 14.167.00 3.781.791.68
0.00
3.38
3.40
3.41
3.53
3.87
3.92
3.95
4.03
4.05
4.26
4.28
4.674.
734.
764.
894.
94
5.675.675.
85
5.89
7.117.12
7.14
7.15
7.167.20
7.22
7.23
7.24
7.25
7.27
7.31
7.37
7.40
7.41
7.47
7.49
7.80
7.83
7.93
8.06
8.09
13C NMR (50.32 MHz, CDCl3) of compound 8b
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
55.3
767
.38
68.6
669
.53
70.5
172
.9873
.18
76.4
777
.10
77.7
478
.80
80.9
2
82.0
197.9
698
.58
104.
46
126.
3412
7.4612
7.58
128.
2412
8.32
128.
4512
9.76
129.
8212
9.99
133.
4113
8.08
138.
80
165.
52165.
6016
5.80
DEPT NMR (50.32 MHz, CDCl3) of compound 8b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
0.0
0.5
1.0
55.3
8
67.12
67.3
6
68.64
69.2
469
.52
70.3
470
.49
70.6
1
72.9773.18
73.4
9
74.81
75.0
7
75.1876
.51
78.8
079
.71
81.9
997.9
4
98.5
5
104.
44
127.
46127.
5812
8.30
128.
3812
9.76
129.
8313
3.43
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
31
1H NMR (200.13 MHz, CDCl3) of compound 8c
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
30.85 10.76 6.606.20 6.012.041.00
0.00
3.35
3.43
3.49
4.38
4.41
4.46
4.63
4.67
4.684.
724.
79
4.95
5.425.
475.
515.86
7.18
7.217.
237.
267.
28
7.34
7.37
7.40
7.43
7.787.91
7.94
7.98
13C NMR (50.32 MHz, CDCl3) of compound 8c
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
56.9
0
68.8
469
.26
70.0
171
.90
73.2
276
.48
77.1
177
.75
78.7
479
.50
82.0
397.9
9
101.
7310
4.24
127.
5912
7.66
128.
3812
9.88
133.
21
138.
6913
8.94
165.
2016
5.88
DEPT NMR (50.32 MHz, CDCl3) of compound 8c
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
56.9
257
.27
67.1568.83
69.2
469
.99
71.8
9
73.21
73.3
0
73.3873.5374.5774.85
75.2
6
78.7
479
.49
82.0
2
97.9
8101.
7210
4.23
127.
5512
7.67
128.
0712
8.38
129.
7812
9.89
133.
2313
3.48
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
32
1H NMR (500.13 MHz, CDCl3) of compound 9a
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
37.10 6.58 5.274.15 2.991.00 0.97
TMS
0.00
3.25
3.46
3.49
3.60
3.62
3.73
3.81
3.81
3.91
4.28
4.41
4.42
4.50
4.52
4.55
4.58
4.70
4.77
4.80
4.94
4.965.05
5.07
7.16
7.17
7.197.
20
7.20
7.23
7.24
7.26
7.31
7.32
7.34
7.35
7.37
13C NMR (125.76 MHz, CDCl3) of compound 9a
200 150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.8
569
.16
71.4
972
.09
72.8
673
.57
75.1
076
.94
77.1
977
.45
82.2
884
.78
99.0
5
104.
25
127.
6012
7.6612
7.98
128.
4013
8.30
138.
3713
8.69
138.
75
DEPT NMR (125.76 MHz, CDCl3) of compound 9a
150 100 50 0
0.0
0.5
1.0
54.8
6
69.12
71.4
8
72.0872.8573.57
74.6
3
74.89
75.0
3
75.1275.83
77.9
980
.33
82.2
784
.77
99.0
4
104.
25
127.
66127.
9912
8.41
128.
48
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
33
1H NMR (200.13 MHz, CDCl3) of compound 9b
8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
28.85 9.528.61 5.15 2.932.08 2.071.01
0.00
2.96
3.67
3.69
3.73
3.75
3.764.44
4.514.66
4.71
4.99
5.59
5.635.
695.
745.865.
91
7.177.18
7.20
7.21
7.227.
247.
267.
27
7.29
7.327.33
7.35
7.45
7.51
7.81
7.87
7.88
7.92
8.00
8.03
13C NMR (50.32 MHz, CDCl3) of compound 9b
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.3
463
.23
71.3
771
.99
72.0
572
.68
74.9
176
.46
77.0
977
.72
80.2
4
98.6
810
1.77
127.
5712
8.34
128.
3812
9.79
129.
8513
3.44
138.
2913
8.37
165.
0616
5.21
165.
9316
6.21
DEPT NMR (50.32 MHz, CDCl3) of compound 9b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.3
4
63.2169.62
69.8
271
.35
71.9
7
72.04
72.1
3
72.67
73.0
274
.28
74.9475
.03
80.2
4
98.6
610
1.77
127.
5812
8.39
129.
8013
3.07
133.
2713
3.46
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
34
1H NMR (500.13 MHz, CDCl3) of compound 10b
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
44.8517.22 5.65 5.532.472.40 2.151.00 0.97
TMS
0.00
3.16
3.18
3.183.
393.
403.
633.
653.
653.
90
4.05
4.07
4.324.35
4.444.47
4.63
4.67
4.79
5.135.
145.
185.
405.
55
5.61
5.63
5.84
6.02
6.04
6.06
7.167.
187.
247.26
7.27
7.277.
287.307.
317.
327.
337.
347.
387.
477.
507.
527.
847.
887.
907.
988.00
13C NMR (125.76 MHz, CDCl3) of compound 10b
150 100 50 00.00
0.05
0.10
0.15
0.20
0.25
55.6
868
.06
69.1
469
.86
70.6
471
.94
72.1
2
74.7
076
.84
77.0
977
.35
79.9
0
97.0
098
.10
101.
36
127.
5112
7.75
128.
3512
8.43
129.
7412
9.98
130.
0613
3.25
133.
43
138.
58
164.
9116
5.09
165.
8916
6.17
DEPT NMR (125.76 MHz, CDCl3) of compound 10b
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.6
8
63.2765.36
68.0
4
68.97
69.1
269
.85
70.6
271
.93
72.10
72.63
72.9
5
74.71
79.9
197.0
098
.09
101.
35
127.
5212
7.76
128.
3012
8.35
129.
8512
9.98
130.
0613
3.27
133.
40
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
35
1H NMR (200.13 MHz, CDCl3) of compound 11
9 8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
34.9514.21 10.77 7.972.75 2.591.720.99
0.00
2.93
3.60
3.65
3.67
3.71
3.73
3.79
3.874.354.
404.
494.
644.
734.87
4.88
5.335.53
5.69
5.735.74
5.81
7.08
7.12
7.167.
207.
227.
237.
267.
297.
307.31
7.32
7.37
7.47
7.49
7.58
7.75
7.887.
987.
997.
998.
03
13C NMR (125.76 MHz, CDCl3) of compound 11
150 100 50 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
54.3
5
61.2
067
.63
69.4
669
.97
71.4
9
72.0
176
.08
76.9
377
.19
77.4
580
.21
98.6
410
1.04
101.
66
127.
5712
8.37
129.
6912
9.85
130.
0613
3.50
138.
34
164.
9216
5.30
165.
4816
5.64
165.
95
DEPT NMR (125.76 MHz, CDCl3) of compound 11
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
54.3
5
61.1962.49
67.6
2
69.46
69.9
671
.48
71.8
6
72.0172.65
73.0
774
.27
74.96
75.0
0
80.2
0
98.6
310
1.04
101.
65
127.
5812
8.33
128.
3812
8.64
129.
6812
9.86
130.
0713
3.45
133.
52
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
36
1H NMR (200.13 MHz, CDCl3) of compound 12
8 7 6 5 4 3 2 1 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
52.3923.92 12.048.753.771.931.00 0.65
0.00
3.39
3.54
3.61
3.74
3.884.
414.
434.
594.
60
4.68
4.885.
125.
145.
405.50
5.72
5.73
5.76
6.02
7.09
7.117.
127.
137.
207.
247.
307.
377.
387.
407.
477.
50
7.61
7.80
7.85
7.93
7.98
7.99
8.008.00
8.03
8.03
13C NMR (50.32 MHz, CDCl3) of compound 12
150 100 50 0
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.7
267
.61
69.2
469
.95
70.6
771
.46
71.8
472
.06
76.9
077
.15
77.4
179
.8397.0
298
.07100.
9910
1.45
127.
5112
7.73
128.
3012
8.36
128.
6412
9.71
129.
7912
9.97
133.
5013
3.60
138.
49
164.
88165.
0716
5.47
165.
89
DEPT NMR (50.32 MHz, CDCl3) of compound 12
150 100 50 0
-0.10
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
55.7
3
61.19
62.44
65.45
67.6
0
68.94
69.9
3
70.6
5
71.4
371
.82
72.06
72.1
5
72.55
73.0
5
74.5
9
74.81
76.0
0
79.8
2
97.0
1
98.0
6
100.
99
101.
44
127.
5112
7.73
128.
31
128.
64
129.
71
129.
79
129.
9713
3.51
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
37
Mass Spectral Characterization Data
Sl. No.
Compound Number
Calculated Mol. Wt.
Observed Mol. Wt.
(M++23 for Na) 1. 1 578.694 601.475 2. 2a 464.55 488.215 3. 2b 506.501 529.383 4. 2f 492.517 515.357 5. 2g 506.501 529.383 6. 2h 506.501 529.380 7. 3a 987.181 1010.029 8. 3b 1029.131 1051.837 9. 4a 432.508 456.378
10. 5a 554.673 577.400 11. 5b 568.699 591.499 12. 5c 582.726 605.583 13. 5d 630.769 653.555 14. 5e 909.291 931.13 15. 5f 580.710 603.529 16. 5g 554.673 577.400 17. 5h 554.673 577.400 18. 5i 554.673 577.400 19. 5j 554.673 577401 20. 6a 608.763 631.403 21. 6b 678.90 701.02 22. 6c 1015.148 1037.901 23. 6d 1029.131 1051.911 24. 7a 1029.131 1051.911 25. 7b 1029.131 1051.911 26. 7c 1029.131 1051.911 27. 8a 1029.131 1051.837 28. 8b 1029.131 1051.911 29. 8c 1029.131 1051.910 30. 9a 987.181 1009.882 31. 9b 1043.115 1065.774 32. 10b 1517.554 1541.203 33. 11 1517.554 1540.074 34. 12 1992.032 2015.441
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
38
UPLC Chromatograms of Crude Reaction Mixtures
For Scheme 1:
Time0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
2.5e+1
3.0e+1
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
2.5e+1
3.0e+1
vsr_scheme1_12h_1 5: Diode Array Range: 3.434e+10.69
3.911.06
0.871.18
vsr_bz_65_6h 5: Diode Array Range: 3.533e+10.74
5.28
Compound 4a m/z=456.378 (M+23 for Na)
Compound 3a m/z=1010.029 (M+23 for Na)
Compound 2b m/z=529.383 (M+23 for Na)
Compound 3b m/z=1051.837 (M+23 for Na)
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
39
Studies on Catalyst optimization UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.02.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.02.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.05.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.05.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.01.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_reaction_4h_8min 5: Diode Array Range: 5.930.75
2.00 5.77
vsr_reaction_16h_8min 5: Diode Array Range: 1.8210.76
0.610.555.67
1.991.33 3.162.44
vsr_AuCl_70_12h 5: Diode Array Range: 5.558e+10.73
4.991.88
vsr_Au2O3_70_12h 5: Diode Array Range: 8.454e+10.75
0.611.97
vsr_Au(pph3)Cl_70_12h 5: Diode Array Range: 8.552e+10.74
1.90
vsr_HAuCl4_70_12h 5: Diode Array Range: 5.883e+10.75
5.56
vsr_AuBr3Et3N_70_12h 5: Diode Array Range: 4.171e+10.77
1.99
vsr_BF3_Et2O_Rt_2h_2 5: Diode Array Range: 3.325e+10.740.58
5.23
vsr_Sc(OTf)3_70_12h 5: Diode Array Range: 6.288e+10.73
4.67
With AuCl3
With AuBr3
With AuCl
With Au2O3
With Au(PPh3)Cl
With HAuCl4
With AuBr3+Et3N
With BF3.Et2O
With Sc(OTf)3
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
40
Gold Activation for Alkyl Glycosides UPLC Chromatograms of Crude Reaction Mixtures
OBnOBnO
OBn
OR1
OBn
5a-5f
+
3b
CatalystOBzOBzO
OMe
OH
2bBzO
AcetonitrileOBnO
BnO
OBn
O
OBn
O
OBzOBz
OMeOBz
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
vsr_OMe_70_24h 5: Diode Array Range: 3.588e+10.75
5.56
vsr_OEt_70_24h 5: Diode Array Range: 2.323e+10.75
5.58
vsr_OiPr_70_24h 5: Diode Array Range: 2.354e+10.75
5.61
vsr_OBn_70_24h 5: Diode Array Range: 2.52e+10.75
vsr_Ocholesterol_70_24h 5: Diode Array Range: 1.524e+10.75
vsr_Oallyl_70_24h 5: Diode Array Range: 2.395e+10.75
R1 = Me
R1 = Et
R1 = iPr
R1 = Bn
R1 = Cholesterol
R1 = Allyl
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
41
Time and Temperature Optimization Studies using AuCl3 UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0
4.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_AuCl3_Rt_24h 5: Diode Array Range: 7.2350.74
1.91
vsr_AuCl3_Rt_48h 5: Diode Array Range: 7.670.74
1.91
vsr_AuCl3_40_12h 5: Diode Array Range: 3.896e+10.74
1.91
vsr_AuCl3_50_12h 5: Diode Array Range: 5.583e+10.74
1.92
vsr_reaction_2h_8min 5: Diode Array Range: 4.4340.75
2.01
vsr_reaction_4h_8min 5: Diode Array Range: 5.930.75
2.005.77
After 24h at rt
After 48h at rt
Then 12h at 40oC
Then 12h at 50oC
Then 12h at 60oC
Then 12h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
42
Time and Temperature Optimization Studies using AuBr3 UPLC Chromatograms of Crude Reaction Mixtures
Time0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
5.0e+1
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
4.0e+1
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_AuBr3_Rt_24h 5: Diode Array Range: 6.9120.74
1.95
vsr_AuBr3_Rt_48h 5: Diode Array Range: 7.7220.74
1.96
vsr_AuBr3_40_12h 5: Diode Array Range: 4.378e+10.74
1.95
vsr_AuBr3_50_12h 5: Diode Array Range: 5.738e+10.75
1.95
vsr_AuBr3_70_12h 5: Diode Array Range: 6.469e+10.74
5.46
vsr_reaction_16h_8min 5: Diode Array Range: 1.6110.76
0.610.55
5.67
1.991.33 3.162.44
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
43
Time and Temperature Optimization Studies using AuCl UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_AuCl_Rt_24h 5: Diode Array Range: 7.7960.72
1.78
vsr_AuCl_Rt_48h 5: Diode Array Range: 7.0140.73
1.85
vsr_AuCl_40_48h 5: Diode Array Range: 5.903e+10.73
1.85
vsr_AuCl_50_12h 5: Diode Array Range: 4.938e+10.73
1.82
vsr_AuCl_60_12h 5: Diode Array Range: 6.002e+10.72
1.78
vsr_AuCl_70_12h 5: Diode Array Range: 5.558e+10.73
4.991.88
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
44
Time and Temperature Optimization Studies using Au2O3
UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_Au2O3_Rt_24h 5: Diode Array Range: 6.960.75
1.97
vsr_Au2O3_Rt_48h 5: Diode Array Range: 6.620.75
1.98
vsr_Au2O3_40_12h 5: Diode Array Range: 6.897e+10.75
1.97
vsr_Au2O3_50_12h 5: Diode Array Range: 5.022e+10.75
1.99
vsr_Au2O3_60_12h 5: Diode Array Range: 6.888e+10.74
1.94
vsr_Au2O3_70_12h 5: Diode Array Range: 8.454e+10.75
0.611.97
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
45
Time and Temperature Optimization Studies using Au(PPh3)Cl
UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
4.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_Au(pph3)Cl_Rt_24h 5: Diode Array Range: 7.9450.73
1.86
vsr_Au(pph3)Cl_Rt_48h 5: Diode Array Range: 7.8060.73
1.87
vsr_Au(pph3)Cl_40_48h 5: Diode Array Range: 4.359e+10.73
1.87
vsr_Au(pph3)Cl_50_12h 5: Diode Array Range: 5.548e+10.74
1.87
vsr_Au(pph3)Cl_60_12h 5: Diode Array Range: 5.9e+10.73
1.84
vsr_Au(pph3)Cl_70_12h 5: Diode Array Range: 8.552e+10.74
1.90
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
46
Time and Temperature Optimization Studies using HAuCl4 UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_HAuCl4_Rt_24h 5: Diode Array Range: 6.9360.75
2.00
vsr_HAuCl4_Rt_48h 5: Diode Array Range: 7.320.74
2.00
vsr_HAuCl4_40_12h 5: Diode Array Range: 3.424e+10.75
1.99
vsr_HAuCl4_50_12h 5: Diode Array Range: 4.816e+10.75
2.00
vsr_HAuCl4_60_12h 5: Diode Array Range: 5.718e+10.75
1.95 5.45
vsr_HAuCl4_70_12h 5: Diode Array Range: 5.883e+10.75
5.56
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
47
Time and Temperature Optimization Studies using AuBr3+Et3N UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
4.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
vsr_AuBr3Et3N_Rt_24h 5: Diode Array Range: 6.770.75
2.01
vsr_AuBr3Et3N_Rt_48h 5: Diode Array Range: 7.4820.77
2.03
vsr_AuBr3Et3N_40_12h 5: Diode Array Range: 3.435e+10.77
2.02
vsr_AuBr3Et3N_50_12h 5: Diode Array Range: 6.008e+10.77
2.03
vsr_AuBr3Et3N_60_12h 5: Diode Array Range: 6.738e+10.77
1.96
vsr_AuBr3Et3N_70_12h 5: Diode Array Range: 4.171e+10.77
1.99
After 24h at rt
Then 12h at 40oC
After 48h at rt
Then 12h at 50oC
Then 12h at 70oC
Then 12h at 60oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
48
Time and Temperature Optimization Studies using AuBr3 using Methyl Mannoside UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
3.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0e+1
4.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
3.0e+1
4.0e+1
vsr_OMe_RT_12h 5: Diode Array Range: 4.712e+10.73
1.83
vsr_OMe_RT_36h 5: Diode Array Range: 3.081e+10.73
1.84
vsr_OMe_65_12h 5: Diode Array Range: 4.966e+10.73
1.81
vsr_OMe_70_24h 5: Diode Array Range: 3.588e+10.75
5.56
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
49
Time and Temperature Optimization Studies using AuBr3 using Ethyl Mannoside UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
3.0e+1vsr_OEt_RT_12h 5: Diode Array
Range: 3.583e+10.74
2.17
vsr_OEt_RT_36h 5: Diode Array Range: 2.359e+10.74
2.17
vsr_OEt_65_12h 5: Diode Array Range: 3.299e+10.73
4.85
vsr_OEt_70_24h 5: Diode Array Range: 2.323e+10.75
5.58
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
50
Time and Temperature Optimization Studies using AuBr3 using Isopropyl Mannoside UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
vsr_OiPr_RT_12h 5: Diode Array Range: 2.777e+10.74
2.55
vsr_OiPr_RT_36h 5: Diode Array Range: 3.127e+10.74
2.56
vsr_OiPr_65_12h 5: Diode Array Range: 2.746e+10.74
5.061.29
vsr_OiPr_70_24h 5: Diode Array Range: 2.354e+10.75
5.61
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
51
Time and Temperature Optimization Studies using AuBr3 using Benzyl Mannoside UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
vsr_OBn_RT_12h 5: Diode Array Range: 2.111e+10.75
vsr_OBn_RT_36h 5: Diode Array Range: 2.28e+10.75
vsr_OBn_65_12h 5: Diode Array Range: 2.812e+10.75
vsr_OBn_70_24h 5: Diode Array Range: 2.52e+10.75
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
52
Time and Temperature Optimization Studies using AuBr3 using Cholesteryl Mannoside
UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5
5.0
7.5
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.0
4.0
6.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
2.5
5.0
7.5
vsr_Ocholesterol_RT_12h 5: Diode Array Range: 1.517e+10.75
vsr_Ocholesterol_RT_36h 5: Diode Array Range: 1.313e+10.75
vsr_Ocholesterol_65_12h 5: Diode Array Range: 1.376e+10.75
vsr_Ocholesterol_70_24h 5: Diode Array Range: 1.524e+10.75
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2009
53
Time and Temperature Optimization Studies using AuBr3 using Allyl Mannoside
UPLC Chromatograms of Crude Reaction Mixtures
Time0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
1.0e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00
AU
0.0
5.0
1.0e+1
1.5e+1
2.0e+1
vsr_Oallyl_RT_12h 5: Diode Array Range: 2.718e+10.75
2.37
vsr_Oallyl_RT_36h 5: Diode Array Range: 2.673e+10.75
2.38
vsr_Oallyl_65_12h 5: Diode Array Range: 2.535e+10.74
5.24
vsr_Oallyl_70_24h 5: Diode Array Range: 2.395e+10.75
After 12h at RT
After 36h at RT
Then 12h at 65oC
Then 24h at 70oC