在烯丙基碳上具有硅基取代的1-氮杂三烯的高度扭矩选择性电环化反应及竞争性的1,7-氢迁移反应
Highly torquoselective electrocyclizations and competing 1,7-hydrogen shifts of 1-azatrienes with silyl substitution at the allylic carbon.
作者信息
Ma Zhi-Xiong, Patel Ashay, Houk K N, Hsung Richard P
机构信息
†Division of Pharmaceutical Sciences, School of Pharmacy, and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705, United States.
‡Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
出版信息
Org Lett. 2015 May 1;17(9):2138-41. doi: 10.1021/acs.orglett.5b00727. Epub 2015 Apr 10.
Abstract
Highly torquoselective electrocyclizations of chiral 1-azatrienes are described. These 1-azatrienes contain an allylic stereocenter that is substituted with a silyl group and are derived in situ from condensation of γ-silyl-substituted enals with vinylogous amides. The ensuing stereoselective ring closures are part of a tandem sequence that constitutes an aza-[3 + 3] annulation method for constructing 1,2-dihydropyridines. Several mechanisms for the formal 1,7-hydrogen shift of these 1-azatrienes were evaluated computationally.
摘要
描述了手性1-氮杂三烯的高度扭矩选择性电环化反应。这些1-氮杂三烯含有一个被硅烷基取代的烯丙基立体中心，并且是通过γ-硅烷基取代的烯醛与烯丙基酰胺的缩合原位衍生而来。随后的立体选择性环化是串联反应序列的一部分，该序列构成了一种用于构建1,2-二氢吡啶的氮杂-[3 + 3]环化方法。通过计算评估了这些1-氮杂三烯形式上的1,7-氢迁移的几种机理。
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