有机金属对映体骨架。连续的半频哪醇/1,5-“类迈克尔”反应作为构建桥头季碳中心氮杂[3.3.1]双环化合物的一种策略方法：应用于（-）-阿达林的全合成。
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.
作者信息
Coombs Thomas C, Zhang Yongqiang, Garnier-Amblard Ethel C, Liebeskind Lanny S
机构信息
Sanford S. Atwood Chemistry Center, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
出版信息
J Am Chem Soc. 2009 Jan 28;131(3):876-7. doi: 10.1021/ja808533z.
Abstract
A nontraditional approach to the enantiocontrolled construction of quaternary center-bearing heteroatom-bridged bicyclo[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.
摘要
报道了一种基于有机金属对映体支架的非传统方法，用于对映体控制构建含季碳中心的杂原子桥连双环[3.3.1]壬烷（高托烷）。该策略利用了TpMo(CO)(2)(5-氧代-η(3)-吡喃基)和TpMo(CO)(2)(5-氧代-η(3)-吡啶基)支架独特的反应特性，并以钼介导的半频哪醇/1,5-“类迈克尔”反应序列来构建季碳中心并合成桥连双环结构。(-)-阿达林的不对称全合成突出了这种方法。
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