博来霉素的全合成。

Total synthesis of borrelidin.

作者信息

Nagamitsu Tohru, Takano Daisuke, Marumoto Kaori, Fukuda Takeo, Furuya Kentaro, Otoguro Kazuhiko, Takeda Kazuyoshi, Kuwajima Isao, Harigaya Yoshihiro, Omura Satoshi

机构信息

School of Pharmacy, Kitasato University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan.

出版信息

J Org Chem. 2007 Apr 13;72(8):2744-56. doi: 10.1021/jo062089i. Epub 2007 Mar 14.

DOI:10.1021/jo062089i

PMID:17355148

Abstract

The total synthesis of borrelidin has been achieved. The best feature of our synthetic route is macrocyclization at C11-C12 for the construction of an 18-membered ring after esterification between two segments. A detailed examination of the macrocyclization led us to the samarium(II) iodide-mediated intramolecular Reformatsky-type reaction as the most efficient synthetic approach. The two key segments were synthesized through regioselective methylation, directed hydrogenation, stereoselective Reformatsky-type reaction, and MgBr2.Et2O-mediated chelation-controlled allylation.

摘要

已完成硼雷素的全合成。我们合成路线的最佳特点是在两个片段酯化后，通过C11 - C12处的大环化构建一个18元环。对大环化的详细研究使我们发现二碘化钐介导的分子内Reformatsky型反应是最有效的合成方法。两个关键片段是通过区域选择性甲基化、定向氢化、立体选择性Reformatsky型反应以及MgBr₂·Et₂O介导的螯合控制烯丙基化反应合成的。