Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan, 48109-1055, USA.
Org Lett. 2010 Mar 5;12(5):1028-31. doi: 10.1021/ol100033s.
A new method for the synthesis of tricyclic nitrogen heterocycles from N,2-diallylaniline derivatives is described. These transformations proceed via sequential alkene aminopalladation of an intermediate L(n)Pd(Ar)(NRR') species followed by alkene carbopalladation of the resulting L(n)Pd(Ar)(R) complex. Both alkene insertion steps occur in preference to C-N or C-C bond-forming reductive elimination. An unusual 1,3-palladium shift occurs when 2-Allyl-N-(2-vinylphenyl)aniline is employed as substrate, which yields a tetracyclic molecule with three contiguous stereocenters.
描述了一种从 N,2-二烯丙基苯胺衍生物合成三环氮杂环化合物的新方法。这些转化通过中间体 L(n)Pd(Ar)(NRR') 物种的顺序烯丙基氨钯化，然后再进行生成的 L(n)Pd(Ar)(R) 配合物的烯丙基碳钯化来进行。两个烯丙基插入步骤都优先于 C-N 或 C-C 键形成的还原消除。当使用 2-烯丙基-N-(2-乙烯基苯基)苯胺作为底物时，会发生异常的 1,3-钯迁移，生成具有三个连续立体中心的四环分子。
