三环烯酮的构建，这是一种用于制备蚜虫二萜烷和蛇床烷B/C/D环系统的常见前体。

Construction of tricyclic enone, a common precursor for aphidicolane and stemodane B/C/D-ring system.

作者信息

Tanaka Tetsuaki, Yamamoto Sachiko, Hiramatsu Kei, Murakami Kazuo, Yoshino Hitoshi, Patra Debasis, Iwata Chuzo, Ohno Hiroaki

机构信息

Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2006 Aug;54(8):1138-43. doi: 10.1248/cpb.54.1138.

DOI:10.1248/cpb.54.1138

PMID:16880658

Abstract

Synthesis of a tricyclic enone (B/C/D ring system), a common key precursor for the aphidicolane- and stemodane-type diterpene, is described. The key reaction for the construction of the quaternary carbon center is allylation of epoxide at the more substituted carbon with an organotitanium reagent. Asymmetric reduction with DIP-Cl followed by stereoselective cyclization of spirocyclic ketone and the functional group modification gave the desired tricyclic enone in good yield.

摘要

描述了一种三环烯酮（B/C/D环系）的合成，它是蚜虫二萜烷型和茎木二萜烷型二萜的常见关键前体。构建季碳中心的关键反应是用有机钛试剂使环氧化物在取代较多的碳上进行烯丙基化反应。用二异丙基氯膦进行不对称还原，随后进行螺环酮的立体选择性环化和官能团修饰，以良好的产率得到了所需的三环烯酮。