A Catalytic, Enantioselective Formal Synthesis of (+)-Dichroanone and (+)-Taiwaniaquinone H

被引：36

作者：

Shockley, Samantha E. ^{[1
]}

Holder, Jeffrey C. ^{[1
]}

Stoltz, Brian M. ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Warren & Katharine Schlinger Lab Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

ORGANIC LETTERS | 2014年 / 16卷 / 24期

关键词：

ASYMMETRIC CONJUGATE ADDITION; TAIWANIA-CRYPTOMERIOIDES; ARYLBORONIC ACIDS; THUJA-STANDISHII; EFFICIENT ROUTE; DITERPENES; (+/-)-DICHROANONE; BARK; (+/-)-TAIWANIAQUINOL-B; CONSTANTS;

D O I：

10.1021/ol5031537

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A catalytic, enantioselective formal synthesis of (+)-dichroanone and (+)-taiwaniaquinone H is reported. The all-carbon quaternary stereocenter was constructed by asymmetric conjugate addition catalyzed by a palladium(II) (S)-tert-butylpyridinooxazoline complex. The unexpected formation of a [3.2.1] bicyclic intermediate required the identification of a new route. Analysis of the Hammett constants for para-substituted arenes enabled the rational design of a highly enantioselective conjugate addition substrate that led to the completion of the formal synthesis.

引用

页码：6362 / 6365

页数：4

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