2008
N. G. Aher et al.
LETTER
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(28) Methyl [20 (21),22]-3b-Acetoxychol-5-trienoate (10)
To a solution of vinyl iodide 9 (0.234 g, 0.5 mmol) in dry
DMF (10 mL), methyl acrylate (0.9 mL 1 mmol), Pd catalyst
(0.005 g, 0.02 mmol), and K2CO3 (0.414 g, 1.5 mmol) were
added, and the reaction mixture was stirred under argon at
25–28 °C for 12 h. Ice was added to the reaction mixture, and
it was extracted with EtOAc (3 × 25 mL). The extract was
washed 5% HCI (2 × 25 mL), sat. aq NaHCO3 (20 mL) and
brine, and dried over Na2SO4. The product was purified by
chromatography on silica gel (2% EtOAc–PE) to give pure
product 10 (0.163 g) in 77% yield and starting material 9
(0.047 g). Colorless solid; mp 93–94 °C; [a]D26 –32.0 (c
2.58, CHCl3); IR (mull): 1691, 1724 cm–1. 1H NMR (200
MHz, CDCl3): d = 0.56 (s, 3 H, 18-CH3), 1.02 (s, 3 H, 19-
CH3), 2.04 (s, 3 H, OCOCH3), 3.76 (s, 3 H, COOCH3), 4.61
(m, 1 H, 3-CH), 5.34 (s, 1 H, 21-CH2), 5.38 (d, J = 5.0 Hz, 1
H, 6-CH), 5.55 (s, 1 H, 21-CH2), 6.02 (d, J = 16.0 Hz, 1 H,
23-CH), 7.36 (d, J = 16.0 Hz, 1 H, 22-CH). 13C NMR (50
MHz, CDCl3): d = 12.8, 19.2, 20.9, 21.3, 24.2, 26.3, 27.6,
31.7, 32.3, 36.5, 36.9, 38.0, 38.6, 43.2, 50.0, 51.1, 51.5, 56.6,
73.8, 117.3, 122.0, 122.3, 139.6, 144.0, 149.1, 167.6, 170.4.
Anal. Calcd for C27H38O4: C, 76.02; H, 8.98. Found: C,
75.79; H, 8.78. ESI-LCMS: m/z = 427.58 [M+ + 1].
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(31) Hydrogenation of Compound 10
To a stirred solution of compound 10 (0.100 g 0.24 mmol) in
MeOH (4 mL) 10% Pd/C (0.015 g, 15% by weight) was
added under an argon-filled balloon. Neat TES (0.4 mL, 2.4
mmol) was added dropwise to the reaction mixture. Within
10 min the reaction was complete. The reaction mixture was
filtered through Celite, and the solvent was removed under
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1985, 26, 4959.
Synlett 2009, No. 12, 2005–2009 © Thieme Stuttgart · New York