Formal Synthesis of (-)-Cephalotaxine

被引：19

作者：

Goncalves-Martin, Monica G. ^{[1
]}

Sigmantas, Sarunas ^{[1
]}

Renaud, Philippe ^{[1
]}

机构：

[1] Univ Bern, Dept Chem & Biochem, CH-3012 Bern, Switzerland

来源：

HELVETICA CHIMICA ACTA | 2012年 / 95卷 / 12期

基金：

瑞士国家科学基金会;

关键词：

Cephalotaxus alkaloids; Azides; Radical reactions; Asymmetric synthesis; Alkaloids; (-)-Cephalotaxine; Self-regeneration of stereogenic centers (SRS); FRIEDEL-CRAFTS CYCLIZATION; HIGHLY EFFICIENT SYNTHESIS; RADICAL CARBOAZIDATION; STEREOSELECTIVE-SYNTHESIS; CEPHALOTAXUS ALKALOIDS; (+/-)-CEPHALOTAXINE; ALCOHOLS; SUBSTITUTION; AZIDATION; SKELETON;

D O I：

10.1002/hlca.201200486

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A formal synthesis of (-)-cephalotaxine (1) by means of a highly stereoselective radical carboazidation process is reported. The synthesis begins with the protected (S)-cyclopent-2-en-1-ol derivative 10 and uses the concept of self-reproduction of a stereogenic center (Schemes 5 and 6). For this purpose, the double bond adjacent to the initial chiral center in 10 is converted into an acetonide after stereoselective dihydroxylation. The initial alcohol function is used to build an exocyclic methylene group suitable for the carboazidation process 8?7 (Scheme 7). Finally the protected diol moiety is converted back to an alkene (14?15?6) and used for the formation of ring B via a Heck reaction (6?(-)-16; Scheme 8).

引用

页码：2502 / 2514

页数：13

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