一种合成（-）-网抑素C11-C23片段的双向方法：高非对映选择性、动力学控制的Meerwein-Ponndorf-Verley还原反应的开发

A two-directional approach to a (-)-dictyostatin C11-C23 segment: development of a highly diastereoselective, kinetically-controlled Meerwein-Ponndorf-Verley reduction.

作者信息

Dilger Andrew K, Gopalsamuthiram Vijay, Burke Steven D

机构信息

Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706-1322, USA.

出版信息

J Am Chem Soc. 2007 Dec 26;129(51):16273-7. doi: 10.1021/ja077336u. Epub 2007 Nov 30.

DOI:10.1021/ja077336u

PMID:18047348

Abstract

A three-step synthesis of a precursor to the C11-C23 segment of (-)-dictyostatin is described. The sequence features a sonication-assisted, enantioselective double hetero Diels-Alder (HDA) reaction catalyzed by Jacobsen's Cr(III) Schiff base catalyst, followed by a novel, highly diastereoselective Meerwein-Ponndorf-Verley (MPV) reduction of the hydropyranone subunits under kinetic control to yield the bis(axial alcohol) 4. Generalized studies of both the HDA and MPV methodologies are also described.

摘要

描述了一种用于合成 (-)-dictyostatin 的 C11-C23 片段前体的三步合成方法。该合成路线的特点是在 Jacobsen 的 Cr(III) 席夫碱催化剂催化下进行超声辅助的对映选择性双杂环 Diels-Alder（HDA）反应，随后在动力学控制下对氢化吡喃酮亚基进行新颖的、高非对映选择性的 Meerwein-Ponndorf-Verley（MPV）还原反应，以生成双（轴向醇）4。还描述了对 HDA 和 MPV 方法的一般性研究。