上海市刑事科学技术研究院刘文斌研究团队，报道了镍催化N-磺酰基苯乙烯基叠氮嘧啶与烷基溴的对映选择性C(sp3) -C (sp3)交叉亲电偶联。相关研究成果发表在2024年9月4日出版的国际学术期刊《美国化学会杂志》。

该文中，研究人员报告了高度对映选择性烷基化氮丙啶开环的第一个例子。

在手性镍/吡啶咪唑啉配合物的催化下，外消旋N-磺酰基苯乙烯基氮丙啶与易得的伯烷基溴之间的不对称C(sp3)–C(sp3)交叉亲电偶联，提供了各种高度富集对映体的苯乙胺衍生物，具有完全的区域控制和良好的官能团耐受性。

初步的机理研究表明了一种由氮丙啶的区域选择性碘解原位，和随后生成的β-氨基苄基碘与烷基溴的对映体偶联组成的反应途径。

附：英文原文

Title: Nickel-Catalyzed Enantioselective C(sp3)–C(sp3) Cross-Electrophile Coupling of N-Sulfonyl Styrenyl Aziridines with Alkyl Bromides

Author: Yun Lan, Qiaoying Han, Pingyong Liao, Ruijia Chen, Fei Fan, Xuejun Zhao, Wenbin Liu

Issue&Volume: September 4, 2024

Abstract: Herein, we report the first example of a highly enantioselective alkylative aziridine ring opening. Under the catalysis of a chiral nickel/pyridine-imidazoline complex, asymmetric C(sp3)–C(sp3) cross-electrophile coupling between racemic N-sulfonyl styrenyl aziridines and readily available primary alkyl bromides furnishes a variety of highly enantioenriched phenethylamine derivatives with complete regiocontrol and good functional group tolerance. Preliminary mechanistic studies support a reaction pathway consisting of regioselective iodolysis of aziridines in situ and subsequent enantioconvergent coupling of the generated β-amino benzyl iodides with alkyl bromides.

DOI: 10.1021/jacs.4c08435

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c08435