(6Z)-和(6E)-克拉迪菌素二萜类化合物合成的通用策略：(-)-克拉迪拉-6,11-二烯-3-醇、(+)-聚海葵素A、(-)-克拉迪尔-11-烯-3,6,7-三醇和(-)-去乙酰氧基阿尔西奥宁乙酸酯的全合成

A general strategy for synthesis of both (6Z)- and (6E)-cladiellin diterpenes: total syntheses of (-)-cladiella-6,11-dien-3-ol, (+)-polyanthellin A, (-)-cladiell-11-ene-3,6,7-triol, and (-)-deacetoxyalcyonin acetate.

作者信息

Kim Hyoungsu, Lee Hyunjoo, Kim Jayoung, Kim Sanghee, Kim Deukjoon

机构信息

Research Institute of Pharmaceutical Sciences, College of Pharmacy, Seoul National University, San 56-1, Shinrim-Dong, Kwanak-Ku, Seoul 151-742, Korea.

出版信息

J Am Chem Soc. 2006 Dec 13;128(49):15851-5. doi: 10.1021/ja065782w.

DOI:10.1021/ja065782w

PMID:17147397

Abstract

The first total synthesis of an (E)-cladiellin diterpene, (-)-cladiella-6,11-diene-3-ol (1), was accomplished featuring an intramolecular amide enolate alkylation-intramolecular Diels-Alder strategy. In addition, a highly stereo-, regio-, and chemoselective synthetic strategy for other members of the cladiellin diterpenes such as (+)-polyanthellin A (2), (-)-cladiell-11-ene-3,6,7-triol (3), and (-)-deacetoxyalcyonin acetate (4) was developed utilizing the synthetic (E)-cladiellin 1 as a common intermediate by taking advantage of the unique chemical properties of its C(6)-(E)-oxatricyclic skeleton.

摘要

通过分子内酰胺烯醇盐烷基化-分子内狄尔斯-阿尔德策略首次全合成了一种（E）-克拉地林二萜，（-）-克拉地拉-6,11-二烯-3-醇（1）。此外，利用合成的（E）-克拉地林1作为共同中间体，借助其C(6)-(E)-氧杂三环骨架的独特化学性质，开发了一种针对其他克拉地林二萜成员的高度立体、区域和化学选择性的合成策略，如（+）-聚海葵素A（2）、（-）-克拉地-11-烯-3,6,7-三醇（3）和（-）-脱乙酰氧基阿尔西奥宁乙酸酯（4）。