（±）-普拉特烯霉素的立体控制形式合成

Stereocontrolled formal synthesis of (+/-)-platensimycin.

作者信息

Matsuo Jun-ichi, Takeuchi Kosuke, Ishibashi Hiroyuki

机构信息

Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.

出版信息

Org Lett. 2008 Sep 18;10(18):4049-52. doi: 10.1021/ol801584r. Epub 2008 Aug 15.

DOI:10.1021/ol801584r

PMID:18702494

Abstract

The caged structure of platensimycin, known as Nicolaou's key intermediate for total synthesis of platensimycin, was synthesized stereoselectively by using the following key steps: (i) diastereoselective Diels-Alder reaction between gamma-benzoyloxy enone and tert-butyldimethylsiloxydiene, (ii) formation of a dihydropyran ring by intramolecular catalytic oxypalladation, and (iii) transannular radical cyclization of monothioacetal with tributyltin hydride and AIBN.

摘要

普拉特烯霉素的笼状结构，即被称为Nicolaou全合成普拉特烯霉素关键中间体的结构，通过以下关键步骤立体选择性合成：(i) γ-苯甲酰氧基烯酮与叔丁基二甲基硅氧基二烯之间的非对映选择性狄尔斯-阿尔德反应；(ii) 通过分子内催化氧钯化形成二氢吡喃环；(iii) 单硫缩醛与三丁基氢化锡和偶氮二异丁腈的跨环自由基环化反应。