合成 Hemicalide 的 C32-C46 片段的研究。C36-C42 亚基相对构型的确定。

Synthetic Studies toward the C32-C46 Segment of Hemicalide. Assignment of the Relative Configuration of the C36-C42 Subunit.

机构信息

†Laboratoire de Chimie Organique, Institute of Chemistry, Biology and Innovation (CBI), ESPCI ParisTech, CNRS (UMR8231), PSL Research University, 10 rue Vauquelin, 75231 Paris Cedex 05, France.

‡Faculté de Pharmacie, Université Paris Descartes, CNRS (UMR8638), 4 avenue de l'observatoire, 75270 Paris Cedex 06, France.

出版信息

Org Lett. 2015 May 15;17(10):2446-9. doi: 10.1021/acs.orglett.5b00955. Epub 2015 Apr 23.

DOI:10.1021/acs.orglett.5b00955

PMID:25906322

Abstract

The synthesis of five diastereomeric model compounds incorporating the C32-C46 segment of the antitumor marine natural product hemicalide has been achieved through a convergent approach relying on the 1,4-addition of an alkenyl boronate to an α,β-unsaturated δ-lactone followed by α-hydroxylation of an enolate and a Julia-Kocienski olefination. Comparison of the (1)H and (13)C NMR data of the model compounds with those of hemicalide enabled the assignment of the relative configuration of the C36-C42 subunit.

摘要

已通过依赖于烯基硼酸对α,β-不饱和δ-内酯的 1,4-加成，随后烯醇化物的α-羟化和 Julia-Kocienski 烯烃化的汇聚方法，合成了包含抗肿瘤海洋天然产物海立得 C32-C46 片段的五个非对映异构体模型化合物。模型化合物的（1）H 和（13）C NMR 数据与海立得的比较，使 C36-C42 亚基的相对构型得以确定。