Evolution of the Total Synthesis of (-)-Okilactomycin Exploiting a Tandem Oxy-Cope Rearrangement/Oxidation, a Petasis-Ferrier Union/Rearrangement, and Ring-Closing Metathesis

被引：50

作者：

Smith, Amos B., III ^{[1
]}

Bosanac, Todd

Basu, Kallol

机构：

[1] Univ Penn, Dept Chem, Penn Ctr Mol Discovery, Philadelphia, PA 19104 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 06期

基金：

美国国家卫生研究院;

关键词：

DIELS-ALDER; CLAISEN REARRANGEMENT; CARBONYL-COMPOUNDS; SELENIUM DIOXIDE; NATURAL-PRODUCTS; ORGANIC HALIDES; OXIDATION; DERIVATIVES; ALDEHYDES; OKILACTOMYCIN;

D O I：

10.1021/ja8084669

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An effective, asymmetric total synthesis of the antitumor antibiotic (-)-okilactomycin (1), as well as assignment of the absolute configuration, has been achieved exploiting a convergent strategy. Highlights of the synthesis include a diastereoselective oxy-Cope rearrangement/oxidation sequence to install the C(1) and C(13) stereogenic centers, a Petasis-Ferrier union/rearrangement to construct the highly functionalized tetrahydropyranone inscribed within the 13-membered macrocycle ring, employing for the first time a sterically demanding acetal, an intramolecular chemoselective acylation to access an embedded bicyclic lactone, and an efficient ring-closing metathesis (RCM) reaction to generate the macrocyclic ring.

引用

页码：2348 / 2358

页数：11

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