SOLVENT EFFECT ON THE BACKBONE REARRANGEMENT OF 3β,4β-EPOXYSHIONANE CATALYZED BY BORON TRIFLUORIDE ETHERATE
作者： Motoo Tori , Kazuo Tachibana , Yoshihiko Moriyama , Takahiko Tsuyuki , Takeyoshi Takahashi
DOI: 10.1246/CL.1976.1359
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摘要: 3β,4β-Epoxyshionane (3) was treated with BF3–Et2O in ether to give D:B-friedo-bacchar-5-en-3β-ol (7), D:B-friedo-bacehar-5(10)-en-3β-ol (8), D:C-friedo-bacchar-7-en-3β-ol (9), and 4α-fluoroshionan-3β-ol (10), besides previously reported dihydrobaccharis oxide (1), while the reaction solvents such as nitromethane, benzene, toluene, hexane, acetonitrile gave no 1. In THF at room temperature, D:B-friedo-type products (7 8) were formed predominantly. The rearrangement low nucleophilicity proceeded up C/D rings; e.g. nitromethane temperature yielded bacchar-12-en-3β-ol (2) D:C-friedo-bacchar-8-en-3β-ol (11). product ratio same various are listed TABLE.
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