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Organic & Biomolecular Chemistry
Page 6 of 10
DOI: 10.1039/C7OB00279C
ARTICLE
Journal Name
(KBr) 3030, 2962, 2866, 1716 cm‐1; 1H‐NMR (300 MHz, CDCl3) 1.24
(s, 9H), 3.78‐3.83 (m, 1H), 3.90‐3.95 (m, 1H), 4.01‐4.07(m, 1H), 4.18‐
4.25 (m, 1H), 4.35‐4.42 (m, 1H), 4.67 (s, 2H x 0.16), 4.71 (br s, 2H x
0.84), 6.19‐6.21 (m, 1H x 0.16), 6.33‐6.35 (m, 1H x 0.84), 7.19‐7.27
(m, 9H); 13C‐NMR (75 MHz, CDCl3) 31.0, 34.3, 64.1, 69.5, 71.9,
76.3, 119.0, 126.0, 127.7, 128.21, 128.28, 128.3, 129.2, 137.3,
138.6, 150.1 (several signals overlapped); HRMS (FAB) m/z calcd for
C21H26NO2Si [M+H]+ 370.1762, found 370.1782.
0.365 mmol), and 4 (14.9 mg, 91.3 μmol) after purification by
column chromatography on silica gel (hexane‐AcOEt, 10/1).
7d: IR (KBr) 3072, 2962, 2858 cm‐1; 1H‐NMR (300 MHz, CDCl3) 1.08
(s, 9H), 1.29 (s, 9H), 1.56 (s, 3H), 3.66 (dd, J = 9.9 and 3.9 Hz, 1H),
3.90 (br, 1H), 4.21 (dd, J = 14.1 and 2.1 Hz, 1H), 4.44‐4.55 (m, 2H),
5.15 (br, 1H), 7.13‐7.70 (m, 14H); 13C‐NMR (75 MHz, CDCl3) 19.1,
20.3, 27.3, 31.2, 34.5, 64.7, 70.8, 71.1, 125.9, 127.4, 127.5, 129.4,
129.5, 131.3, 133.9, 135.70, 135.73, 150.4 (several signals
overlapped); HRMS (EI) m/z calcd for C32H42NO2SSi531.2627, found
531.2608
N‐{4‐[(4‐tert‐Butylphenylthio)methylene]tetrahydrofuran‐3‐yl}‐O‐
(tert‐butyldiphenylsilyl)hydroxylamine (7b). (Table 1, entry 4).
Following General Procedure, 7b (67.0 mg, 81%, E/Z = 11/89) was
obtained from 2b (57.5 mg, 0.159 mol), 5 (60.4 L, 0.350 mmol),
8d: IR (KBr) 3072, 2961, 2856 cm‐1; 1H‐NMR (300 MHz, CDCl3) 1.10
(s, 9H), 12.8 (s, 9H), 1.65 (s, 3H), 3.06 (d, J = 9.3 Hz, 1H), 3.39 (dd, J =
11.4 and 2.1 Hz, 1H), 3.91 (s, 1H), 4.50 (d, J = 11.4 Hz, 1H), 5.49 (d, J
= 10.2 Hz, 1H), 7.09‐7.76 (m, 14H); 13C‐NMR (75 MHz, CDCl3) 18.7,
19.2, 27.4, 31.2, 34.4, 61.0, 64.2, 68.7, 126.1, 127.4, 127.5, 128.5,
129.46, 129.49, 129.6, 130.1, 133.9, 135.2, 135.4, 135.7, 135.9,
149.8; HRMS (FAB) m/z calcd for C32H40NO2SSi [M+H]+ 532.2706,
found 532.2656
and
4 (13.0 mg, 79.5 mol) after purification by column
chromatography on silica gel (hexane‐AcOEt, 25/1). All data were
described without distinction of the two diastereomers. IR (KBr)
1
3072, 2961, 2932, 2856 cm‐1; H‐NMR (300 MHz, CDCl3) 1.10 (s,
9H x 0.89), 1.12 (s, 9H x 0.11), 1.30 (s, 9H x 0.11), 1.31 (s, 9H x 0.89),
3.73‐3.81 (m, 1H + 2H x 0.89), 4.05‐4.40 (m, 2H x 0.11 + 2H x 0.89 +
2H x 0.11), 5.17 (br, 1H x 0.89), 5.48 (br, 1H x 0.11), 6.24 (s, 1H x
0.11), 6.29 (s, 1H x 0.89), 7.21‐7.41 (m, 14H); 13C‐NMR (75 MHz,
CDCl3) 19.0, 19.2, 26.6, 27.4, 29.7, 31.3, 34.5, 64.5, 65.8, 69.7,
71.2, 71.4, 71.6, 119.2, 119.4, 126.1, 127.5, 127.7, 129.1, 129.2,
129.6, 131.8, 133.7, 135.7, 135.9, 138.5, 150.1; HRMS (FAB) m/z
calcd for C31H39NO2SSi [M+H]+ 517.2471, found 517.2567.
N‐{4‐[(E)‐1‐(4‐tert‐Buthylphenylthio)ethylidene]‐1‐tosylpyrrolidin‐
3‐yl}‐O‐(tert‐buthyldiphenylsilyl)hydroxylamine (7e) and
N‐[5‐(4‐tert‐Butylphenylthio)‐4‐methyl‐1‐tosyl‐1,2,3,6‐
tetrahydropyridin‐3‐yl]‐O‐(tert‐butyldiphenylsilyl)hydroxylamine
(8e) (Table 2, entry 2).
N‐{4‐[(4‐tert‐Butylphenylthio)methylene]‐1‐tosylpyrrolidin‐3‐yl}‐
O‐(tert‐butyldiphenylsilyl)hydroxylamine (7c) (Table 1, entry 5).
Following General Procedure, 7c (70.3 mg, 63%, E/Z = 20/80) was
obtained from 3c (84.4 mg, 0.167 mol), 5 (63.5 L, 0.368 mmol),
and 4 (46.6 mg, 0.284 mmol) after purification by column
chromatography on silica gel (hexane‐CH2Cl2, 1/2 then hexane‐
Following General Procedure, 7e (12.7 mg, 11%) and 8e (70.4 mg,
63%) were obtained from 3e (84.5 mg, 0.163 mmol), 5 (61.8 μL,
0.358 mmol), and 4 (14.7 mg, 89.5 μmol) after purification by
column chromatography on silica gel (hexane‐CH2Cl2, 1/2 then
hexane‐AcOEt, 5/1).
1
AcOEt, 25/1). IR (KBr) 2963, 2858, 2349 cm‐1; H‐NMR (300 MHz,
CDCl3) 1.04 (s, 9H x 0.2), 1.06 (s, 9H x 0.8), 1.29 (s, 9H x 0.2), 1.31
(s, 9H x 0.8), 2.41 (s, 3H x 0.2), 2.43 (s, 3H x 0.8), 3.12‐3.28 (m, 1H x
0.8, 1H x 0.2), 3.56‐3.88 (m, 1H x 0.8 x 3, 1H x 0.2 x 3, 1H x 0.8), 4.16
(br, 1H x 0.2), 5.00 (d, J = 10.9 Hz, 1H x 0.8), 5.33 (d, J = 8.1 Hz, 1H x
0.2), 6.12 (s, 1H x 0.8), 6.29 (s, 1H x 0.2), 7.13‐7.72 (m, 18H); 13C‐
NMR (75 MHz, CDCl3) 19.1, 21.5, 27.2, 27.3, 31.2, 34.5, 50.2, 50.9,
51.5, 52.4, 63.1, 64.5, 122.4, 122.7, 126.1, 126.2, 127.5, 127.6,
127.7, 127.9, 129.3, 129.6, 129.7, 131.1, 131.7, 132.2, 133.2, 133.4,
133.5, 134.9, 135.4, 135.7, 135.9, 143.7, 143.8, 150.3, 150.4; HRMS
(EI) m/z calcd for C38H46N2O3S2Si 670.2719, found 670.2711.
1
7e: IR (KBr) 2961, 2858 cm‐1; H‐NMR (300 MHz, CDCl3) 1.07 (s,
9H), 1.29 (s, 9H, 3H), 2.44 (s, 3H), 2.90 (dd, J = 5.1 and 10.3 Hz, 1H),
3.58 (d, J = 14.7 Hz, 1H), 3.80 (br, 1H), 4.05 (d, J = 14.7 Hz, 1H), 4.22
(d, J = 10.3 Hz, 1H), 4.96 (br, 1H), 7.08‐7.77 (m, 18H); 13C‐NMR (75
MHz, CDCl3) 19.2, 19.4, 21.6, 27.0, 27.3, 31.2, 50.9, 51.4, 63.4,
126.0, 127.5, 127.6, 127.7, 128.1, 128.6, 129.6, 129.7, 131.8, 132.1,
133.4, 134.8, 135.5, 135.7, 135.8, 143.7 (several signals
overlapped); HRMS (EI) m/z calcd for C39H48N2O3S2Si 684.2876,
found 684.2875.
N‐{4‐[1‐(4‐tert‐Butylphenylthio)ethylidene]tetrahydrofuran‐3‐yl}‐
O‐(tert‐butyldiphenylsilyl)hydroxylamine (7d) and
1
8e: IR (KBr) 2961, 2856, cm‐1; H‐NMR (300 MHz, CDCl3) 1.12 (s,
9H), 1.29 (s, 9H), 1.60 (s, 3H), 2.39 (s, 3H), 2.41 (d, J = 11.0 Hz, 1H),
3.10 (d, J = 16.1 Hz, 1H), 3.25 (d, J = 9.5 Hz, 1H), 3.86 (d, J = 16.1 Hz,
1H), 4.39 (d, J = 11.7 Hz, 1H), 5.35 (d, J = 10.6 Hz, 1H), 7.03‐7.77 (m,
18H); 13C‐NMR (75 MHz, CDCl3) 18.9, 19.2, 21.5, 27.3, 31.2, 34.5,
43.5, 48.9, 61.9, 126.0, 126.2, 127.4, 127.6, 127.7, 129.4, 129.6,
133.5, 133.6, 133.7, 135.7, 135.9, 136.0, 143.7, 150.0; HRMS (EI)
m/z calcd for C39H48N2O3S2Si 684.2876, found 684.2890.
N‐[5‐(4‐tert‐Butylphenylthio)‐4‐methyl‐3,6‐dihydro‐2H‐pyran‐3‐
yl]‐O‐(tert‐butyldiphenylsilyl)hydroxylamine (8d) (Table 2, entry
1).
Following General Procedure, 7d (6.3 mg, 7%) and 8d (61.0 mg,
69%) were obtained from 3d (60.7 mg, 0.166 mmol), 5 (63.0 μL,
6 | J. Name., 2012, 00, 1‐3
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