First total synthesis of modiolide A, based on the whole-cell yeast-catalyzed asymmetric reduction of a propargyl ketone

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• 作者：Masaaki Matsuda ; Takahiro Yamazaki ; Ken-ichi Fuhshuku ; Takeshi Sugai
• 关键词：Palladium ; Allylic substitution ; Allylation ; Boronic acid ; Cross-coupling ; Arylation ; Microwave irradiation
• 刊名：Tetrahedron
• 出版年：2007
• 期刊代码：107_00404020
• 类别：ch
• 出版时间：3 September 2007
• 卷：63
• 期：36
• 页码：8752-8760
• 文件大小：327 K

摘要

While the first total synthesis of modiolide A (1a), a 10-membered ring lactone with a marine-origin was achieved, an important chiral building block for constructing the chirality at C-4 in 1a, (S)-6-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (3a) was obtained in as high as 96.1%ee. Asymmetric reduction of a silylated propargyl ketone (5) mediated by whole-cell of Pichia minuta IAM 12215 was established. This yeast-mediated reduction was also applicable to provide stereochemically pure (3S,5R)-5-[(4-methoxybenzyl)oxy]-1-trimethylsilyl-1-hexyn-3-ol (15), a synthetic intermediate for the related 10-membered lactone, tuckolide (16).