金属卟啉催化的烯丙基取代烯烃的非对映选择性环氧化反应。

Metalloporphyrin-catalyzed diastereoselective epoxidation of allyl-substituted alkenes.

作者信息

Chan Wing-Kei, Wong Man-Kin, Che Chi-Ming

机构信息

Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong, China.

出版信息

J Org Chem. 2005 May 27;70(11):4226-32. doi: 10.1021/jo047733c.

DOI:10.1021/jo047733c

PMID:15903294

Abstract

By using [Mn(2,6-Cl(2)TPP)Cl] (1) as a catalyst and Oxone/H(2)O(2) as an oxidant, we have developed an efficient method for erythro-selective epoxidation of acyclic allyl-substituted alkenes, including allylic alcohols, amines, and esters. Up to 9:1 erythro selectivities for terminal allyllic alkenes could be achieved, which are significantly higher than that achieved using m-CPBA as an oxidant. In addition, the synthetic utilities of this epoxidation method were highlighted in stereoselective synthesis of key anti-HIV drug intermediates and epoxidation of glycals.

摘要

通过使用[Mn(2,6-Cl(2)TPP)Cl]（1）作为催化剂，过氧单磺酸钾/过氧化氢作为氧化剂，我们开发了一种高效的方法用于非环状烯丙基取代烯烃（包括烯丙醇、胺和酯）的赤式选择性环氧化反应。对于末端烯丙基烯烃，可实现高达9:1的赤式选择性，这显著高于使用间氯过氧苯甲酸作为氧化剂时所达到的选择性。此外，这种环氧化方法的合成实用性在关键抗HIV药物中间体的立体选择性合成以及糖烯的环氧化反应中得到了突出体现。