European Journal of Organic Chemistry
10.1002/ejoc.201700461
2
.10–2.07 (m, 1H, H-4a), 2.05–1.98 (m, 1H, CH CH OTBS), 1.89 (dd, J = 14.0 Hz, J = 6.2 Hz, 1H,
2 2
H-4 ), 1.43–1.37 (m, 1H, CH CH OTBS), 1.36–1.33 (m, 1H, H-4 ), 0.87 (s, 9H, C(CH ) ), 0.01 (s,
a
2
2
b
3 3
1
3
6
1
H, Si(CH ) ) ppm; C NMR, HSQC, HMBC (100.6 MHz, CDCl ) = 131.2 (C-6), 127.3 (C-5),
3
2
3
03.7 (C-1), 91.5 (C-6b), 73.8 (C-6a), 73.2 (C-3), 64.8 (C-3a), 61.4 (CH CH OTBS), 56.9 (C-6b-
2
2
OCH ), 55.6 (C-1-OCH ), 36.2 (CH CH OTBS), 36.2 (C-4a), 35.1 (C-4b), 30.9 (C-4), 26.1 (3C,
3
3
2
2
C(CH ) ), 18.4 (C(CH ) ), –5.3 (2C, Si(CH ) ) ppm; ESI-HRMS calcd for [C H O Si + Na]
3
3
3 3
3 2
20 34
4
3
89.2124 , found 389.2142.
rac-tert-Butyl{2-[(1S,3aS,5aR,8aR)-1,5a-dimethoxy-8-(phenylsulfanyl)-4,5,5a,8-
tetrahydropentaleno[1,6a-c]furan-3a(3H)-yl]ethoxy}dimethylsilane (15)
To a solution of the photoproduct 9a (113 mg, 0.309 mmol) in CH Cl (10 mL) were added
2
2
thiophenol (119 mg, 1.08 mmol) and triethylborane (1 M in hexane, 0.15 mL, 0.150 mmol) and the
mixture was stirred for 18 h at room temperature under air atmosphere. The reaction was quenched
with aqueous NaOH (4 M, 10 mL) and extracted with CH Cl (2 × 10 mL). The combined organic
2
2
layers were dried over Na SO and evaporated. After purification by column chromatography
2
4
(
cyclohexane + 2% NEt ) the title compound (66.7 mg, 46%) was obtained as a colorless oil:
3
R = 0.28 (cyclohexane/EtOAc 10:1); IR (ATR) 휈̃ = 2931, 1583, 1472, 1345, 1254, 1091, 965, 833,
f
–
1 1
7
7
75, 740, 691 cm ; H NMR, COSY (400 MHz, CDCl ) = 7.44–7.41 (m, 2H, Ph-H2,6), 7.28–
3
.24 (m, 2H, Ph-H3,5), 7.18–7.14 (m, 1H, Ph-H4), 6.08 (dd, J = 5.7 Hz, J = 3.0 Hz, 1H, H-7), 5.69
(
d, J = 5.7 Hz, 1H, H-6), 5.10 (s, 1H, H-1), 4.18 (d, J = 3.0 Hz, 1H, H-8), 4.06 (dd, J = 8.8 Hz,
J = 1.7 Hz, 1H, H-3 ), 3.69–3.64 (m, 2H, CH CH OTBS), 3.62–3.55 (m, 1H, H-3 ), 3.35 (s, 3H, C-
a
2
2
b
5
a-OCH ), 3.14 (s, 3H, C-1-OCH ), 1.96–1.81 (m, 3H, H-4 , H-5), 1.68 (dd, J = 12.6 Hz,
3 3 a
J = 5.7 Hz, 1H, CH CH OTBS), 1.42–1.37 (m, 1H, H-4 ), 1.21–1.12 (m, 1H, CH CH OTBS), 0.89
2
2
b
2
2
1
3
(
s, 9H, C(CH ) ), 0.04 (s, 6H, Si(CH ) ) ppm; C NMR, HSQC, HMBC (100.6 MHz, CDCl )
3 3 3 2 3
= 138.2 (Ph-C1), 136.4 (C-7), 132.9 (C-6), 130.1 (2C, Ph-C2,6), 128.6 (2C, Ph-C3,5), 125.9 (Ph-
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