echinopines A 和 B 的全合成：利用生物启发的晚期分子内环丙烷化反应。

Total synthesis of echinopines A and B: exploiting a bioinspired late-stage intramolecular cyclopropanation.

机构信息

Chemical Synthesis Laboratory@Biopolis, Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), 11 Biopolis Way, The Helios Block, #03-08, Singapore 138667.

出版信息

Org Lett. 2011 Nov 4;13(21):5724-7. doi: 10.1021/ol202053m. Epub 2011 Sep 1.

DOI:10.1021/ol202053m

PMID:21882829

Abstract

Total synthesis of echinopine A and B have been accomplished, based on a strategy that involved two transition-metal-mediated ene-yne cycloisomerizations. A modified Pd-catalyzed enyne cycloisomerization/intramolecular Diels-Alder cascade rendered a more streamlined synthesis of tricyclic ketone 15, and a Ru-catalyzed ene-yne cycloisomerization/cyclopropanation resembled the late-stage [5/7] → [3/5/5/7] ring-forming sequence in the proposed biosynthetic pathway.

摘要

基于涉及两种过渡金属介导的烯炔环异构化反应的策略，已经完成了海猪豆碱 A 和 B 的全合成。改进的 Pd 催化的烯炔环异构化/分子内 Diels-Alder 级联反应使得三环酮 15 的合成更加流畅，而 Ru 催化的烯炔环异构化/环丙烷化反应类似于所提出的生物合成途径中的晚期 [5/7]→[3/5/5/7]环形成序列。