一种用于合成完整的邻位双四氢呋喃番荔枝内酯文库的双向方法。

A bidirectional approach to the synthesis of a complete library of adjacent-bis-THF annonaceous acetogenins.

作者信息

Das Sanjib, Li Lian-Sheng, Abraham Sunny, Chen Zhiyong, Sinha Subhash C

机构信息

The Skaggs Institute for Chemical Biology and the Department of Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.

出版信息

J Org Chem. 2005 Jul 22;70(15):5922-31. doi: 10.1021/jo050697c.

DOI:10.1021/jo050697c

PMID:16018687

Abstract

Thirty-six stereoisomers of bifunctional adjacent bis-THF (tetrahydrofuran) lactones have been synthesized, which can afford a complete library of the adjacent bis-THF Annonaceous acetogenins. The bis-THF lactones were synthesized, starting from the enantioselectively pure 8,9:12,13-(E,E and Z,E)-16-benzyloxy-5-hydroxy-hexadeca-1,4-olide, in a highly distereoselective manner using oxidative reactions, including rhenium(VII) oxides-mediated oxidative cyclization, Shi's asymmetric epoxidation, and Sharpless asymmetric dihydroxylation reactions. Using the nonsymmetrical bis-THF lactones, syntheses of two nonnatural acetogenins were achieved.

摘要

已合成了36种双官能团邻位双四氢呋喃内酯的立体异构体，它们能够提供完整的邻位双四氢呋喃番荔枝内酯文库。双四氢呋喃内酯的合成起始于对映体纯的8,9:12,13-（E，E和Z，E）-16-苄氧基-5-羟基-十六碳-1,4-内酯，采用氧化反应，包括铼（VII）氧化物介导的氧化环化、史氏不对称环氧化和夏普莱斯不对称双羟基化反应，以高度非对映选择性的方式进行。利用非对称双四氢呋喃内酯，实现了两种非天然产乙酸菌素的合成。