Total Synthesis of Neodolastane Diterpenes Trichoaurantianolides C and D

被引:7
|
作者
Williams, David R. [1 ]
Gladen, Paul T. [1 ]
Pinchman, Joseph R. [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
来源
JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 11期
基金
美国国家科学基金会;
关键词
ENANTIOSELECTIVE TOTAL-SYNTHESIS; REGIOSELECTIVE HYDROSTANNATIONS; TRICHOLOMA-AURANTIUM; COPRINUS-HEPTEMERUS; EFFICIENT CATALYST; SECONDARY ALCOHOLS; CARBON SKELETON; GUANACASTEPENE; KETONES; CYCLIZATION;
D O I
10.1021/acs.joc.5b00355
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The first total synthesis of trichoaurantianolides C and D is described. An enantiocontrolled pathway leads to rapid construction of the tricyclic carbon skeleton and establishes the trans-dimethyl geometry of the quaternary bridgehead carbons Via a reductive cyclization. Application of the pi-allyl Stile cross-coupling leads to a nonracermic allylic alcohol as a prerequisite for the introduction of asymmetry in the cycloheptane system. Two strategies have been examined for elaboration of the unsaturated tetrahydrofuranyl ring from a common tricyclic intermediate. These efforts reveal a number of unanticipated issues of reactivity and significant stereochemical requirements for a novel acyloin rearrangement as well as the elimination and cycloclehydration of chiral alpha-hydroxy ketones. Key reactions leading to completion of the synthesis include the stereoselective addition of isopropenyllithium TMEDA complex and a, facile chemoselective oxidation with Selenium dioxide.
引用
收藏
页码:5474 / 5493
页数:20
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