2,3-二氧杂双环[2.2.2]辛烷-5,6-二醇的合成与化学性质

Synthesis and chemistry of 2,3-dioxabicyclo[2.2.2]octane-5,6-diols.

作者信息

Valente Peter, Avery Thomas D, Taylor Dennis K, Tiekink Edward R T

机构信息

Department of Chemistry, The University of Adelaide, South Australia 5005, Australia.

出版信息

J Org Chem. 2009 Jan 2;74(1):274-82. doi: 10.1021/jo8020506.

DOI:10.1021/jo8020506

PMID:19035821

Abstract

1,4-Disubstituted 2,3-dioxabicyclo[2.2.2]oct-5-enes were dihydroxylated with osmium tetroxide to yield diols anti to the peroxide linkage in a highly selective manner. Reduction of the peroxide bond furnished cyclohexane-1,2,3,4-tetraols with toxocarol relative stereochemistry in excellent yield. This new methodology was employed to synthesize the natural product (1S,2R,3S,4R,5R)-2-methyl-5-(propan-2-yl)cyclohexane-1,2,3,4-tetrol (1) in a short sequence from (R)-alpha-phellandrene. Moreover, during the study of the chemistry of 2,3-dioxabicyclo[2.2.2]octane-5,6-diols a hitherto unknown rearrangement was discovered which has wide applicability for the synthesis of 1,4-dicarbonyls, including optically enriched synthons. A broad range of mechanistic investigations applicable to this rearrangement are also reported.

摘要

1,4-二取代的2,3-二氧杂双环[2.2.2]辛-5-烯用四氧化锇进行二羟基化反应，以高选择性方式生成与过氧化物键呈反式的二醇。过氧化物键的还原以优异的产率提供了具有毒胡萝卜醇相对立体化学的环己烷-1,2,3,4-四醇。这种新方法被用于从(R)-α-水芹烯以短路线合成天然产物(1S,2R,3S,4R,5R)-2-甲基-5-(丙烷-2-基)环己烷-1,2,3,4-四醇(1)。此外，在对2,3-二氧杂双环[2.2.2]辛烷-5,6-二醇的化学研究过程中，发现了一种迄今未知的重排反应，该反应在包括光学富集合成子在内的1,4-二羰基化合物的合成中具有广泛的适用性。还报道了适用于这种重排反应的广泛的机理研究。