An improved synthesis of a key intermediate for (+)-biotin from d-mannose
- 作者：Fen-Er Chen ; Jian-Feng Zhao ; Fang-Jun Xiong ; Bin Xie ; Ping Zhang
- 关键词：(+)-Biotin ; Methyl 2 ; 3 ; 4 ; 5-tetradeoxy-7 ; 8-O-isopropylidene-d-arabino-nanonate ; d-Mannose ; Horner– ; Emmons olefination ; Chiral pool
- 刊名：Carbohydrate Research
- 出版年：2007
- 期刊代码：15_00086215
- 类别：ch
- 出版时间：26 November 2007
- 卷：342
- 期：16
- 页码：2461-2464
- 文件大小：131 K
摘要
An efficient and reproducible process for the synthesis of methyl 2,3,4,5-tetradeoxy-7,8-O-isopropylidene-d-arabino-nanonate (2), a key intermediate in the total synthesis of (+)-biotin (1), starting from readily available d-mannose is described. The crucial part of this synthesis was the development of a practical route to a novel O-benzyl protected unsaturated ester methyl (benzyl 5,6,7,8-tetradeoxy-2,3-O-isopropylidene-α-d-lyxo-nona-5,7-dienofuranosid) uronate (7), allowing the one-step preparation of hydroxy ester methyl 5,6,7,8-tetradeoxy-2,3-O-isopropylidene-α-d-lyxo-nanofuranuronate (8) by the catalytic debenzylation and hydrogenation over palladium on carbon catalyst. This procedure requires no chromatographic purification, which makes it ideal for synthetic preparation on an industrial scale.