手性 OsO4 催化的 1,5-二烯的立体选择性氧化环化反应。

Stereoselective OsO4-catalyzed oxidative cyclization of 1,5-dienes.

机构信息

Technische Universität Dresden, 01062 Dresden, Germany.

出版信息

J Org Chem. 2010 Mar 19;75(6):1967-73. doi: 10.1021/jo100147e.

PMID:20180518

Abstract

The mechanism of the oxidation of 1,5-dienes with osmium tetroxide was investigated by density functional theory calculations (B3LYP/6-311+G*). The observed products, 2,5-bis(hydroxymethyl)tetrahydrofurans, are formed stereoselectively in a concerted reaction. Enantioselectivity could be induced by an enantioselective dihydroxylation followed by condensation of the 5,6-dihydroxyolefine with osmium tetroxide, while the diastereoselectivity is achieved by reaction of the 1,5-diene with osmium tetroxide and intermediate reoxidation of the osmium(VI) ester.

摘要

通过密度泛函理论计算（B3LYP/6-311+G*）研究了锇四氧化物氧化 1,5-二烯的机理。观察到的产物 2,5-双（羟甲基）四氢呋喃以协同反应立体选择性地形成。通过对 5,6-二羟基烯烃进行对映选择性二羟基化反应，然后与锇四氧化物缩合，可以诱导对映选择性，而通过 1,5-二烯与锇四氧化物反应和中间锇（VI）酯的再氧化，可以实现非对映选择性。