Sherry Benjamin D, Loy Rebecca N, Toste F Dean
Center for New Directions in Organic Synthesis, Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA.
J Am Chem Soc. 2004 Apr 14;126(14):4510-1. doi: 10.1021/ja031895t.
A mild method for the synthesis of 2-deoxysugars from the coupling of glycals with a range of nucleophiles is described. The method employs 1 mol % of an air- and moisture-tolerant rhenium-oxo complex [ReOCl3(SMe2)(Ph3PO)] as a catalyst for the formation of O-, N-, and S-alpha-glycosides. The catalytic system tolerates a number of commonly employed protecting groups, including isopropylidene acetals, alkyl and silyl ethers, acetates, and benzoates. Furthermore, the high-oxidation-state complex selectively catalyzes the coupling with the glycal acceptor in preference to oxidation of the glycals, alcohols, and even thiols.
描述了一种由糖烯与一系列亲核试剂偶联合成2-脱氧糖的温和方法。该方法使用1 mol%的耐空气和湿气的铼-氧配合物[ReOCl3(SMe2)(Ph3PO)]作为催化剂来形成O-、N-和S-α-糖苷。该催化体系能耐受多种常用的保护基，包括异亚丙基缩醛、烷基和硅基醚、乙酸酯和苯甲酸酯。此外，高氧化态的配合物优先选择性地催化与糖烯受体的偶联反应，而不是糖烯、醇甚至硫醇的氧化反应。
