Stereoselective Anti-Markovnikov Geminal Diamination and Dioxygenation of Vinylarenes Mediated by the Bromonium Ion
Stereoselective Anti-Markovnikov Geminal Diamination and Dioxygenation of Vinylarenes Mediated by the Bromonium Ion
复制标题
DOI：
10.1002/ejoc.201600203
复制
发表时间：
2016-05-01
影响因子：
2.8
通讯作者：
Chandrasekaran, Srinivasan
中科院分区：
文献类型：
--
作者：
Balaji, Pandur Venkatesan;Chandrasekaran, Srinivasan
报道了溴离子介导的乙烯基芳烃的立体选择性反马氏偕二胺化和化学计量偕双加氧反应。已经描述了亲核试剂上的取代基的作用以及杂原子的亲核性在竞争的成对和邻位加成途径中的作用。孪位双加氧反应的立体选择性取决于产物环的大小和引起立体选择性的取代基的位置。氘标记研究的结果证实了在偕加成过程中苯基通过半频哪醇重排的迁移。
A straightforward method is reported for the stereoselective anti-Markovnikov geminal diamination and stoichiometric geminal dioxygenation of vinylarenes mediated by a bromonium ion. The role of the substituent on the nucleophile and the nucleophilicity of the heteroatom in the competing geminal and vicinal addition pathways has been described. The stereoselectivity of the geminal dioxygenation is dependent on the ring size of the product and the position of the substituent that induces the stereoselectivity. The migration of the phenyl group through a semi-pinacol rearrangement during the geminal addition process was confirmed by the results of deuterium labelling studies.