Organic Chemistry Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune-, 411008, India.
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-, 201002, India.
Angew Chem Int Ed Engl. 2019 Oct 1;58(40):14104-14109. doi: 10.1002/anie.201906681. Epub 2019 Aug 29.
A phosphite-mediated [2,3]-aza-Wittig rearrangement has been developed for the regio- and enantioselective allylic alkylation of six-membered heteroaromatic compounds (azaarenes). The nucleophilic phosphite adducts of N-allyl salts undergo a stereoselective base-mediated aza-Wittig rearrangement and dissociation of the chiral phosphite for overall C-H functionalization of azaarenes. This method provides efficient access to tertiary and quaternary chiral centers in isoquinoline, quinoline, and pyridine systems, tolerating a broad variety of substituents on both the allyl part and azaarenes. Catalysis with chiral phosphites is also demonstrated with synthetically useful yields and enantioselectivities.
亚膦酸盐介导的[2,3]-氮杂-Wittig 重排已被开发用于六元杂芳族化合物（氮杂芳烃）的区域和对映选择性烯丙基烷基化。N-烯丙基盐的亲核亚膦酸盐加合物经历立体选择性碱介导的氮杂-Wittig 重排和手性亚膦酸盐的解离，用于氮杂芳烃的整体 C-H 官能化。该方法为异喹啉、喹啉和吡啶体系中的叔和季手性中心提供了有效的途径，对烯丙基部分和氮杂芳烃上的各种取代基都具有良好的耐受性。手性亚膦酸盐的催化作用也具有合成上有用的产率和对映选择性。
