Organometallic Enantiomeric Scaffolding. Sequential Semipinacol/1,5-"Michael-like" Reactions as a Strategic Approach to Bridgehead-Quaternary Center Aza[3.3.1]Bicyclics: Application to the Total Synthesis of (-)-Adaline
Organometallic Enantiomeric Scaffolding. Sequential Semipinacol/1,5-"Michael-like" Reactions as a Strategic Approach to Bridgehead-Quaternary Center Aza[3.3.1]Bicyclics: Application to the Total Synthesis of (-)-Adaline
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DOI：
10.1021/ja808533z
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发表时间：
2009-01-28
影响因子：
15
通讯作者：
Liebeskind, Lanny S.
中科院分区：
文献类型：
--
作者：
Coombs, Thomas C.;Zhang, Yongqiang;Liebeskind, Lanny S.
A nontraditional approach to the enantiocontrolled construction of quaternary center-bearing heteroatom-bridged bicycto[3.3.1]nonanes (homotropanes) is reported that is based on organometallic enantiomeric scaffolding. This strategy takes advantage of the unique reactivity profiles of TpMo(CO)(2)(5-oxo-eta(3)-pyranyl) and TpMo(CO)(2)(5-oxo-eta(3)-pyridinyl) scaffolds, and features a molybdenum-mediated semipinacol/1,5-"Michael-like" reaction sequence to establish the quaternary center and synthesize the bridged bicyclic structure. An asymmetric total synthesis of (-)-adaline highlights this methodology.
