EaStCHEM School of Chemistry, The University of Edinburgh , The King's Buildings, David Brewster Road, Edinburgh EH9 3FJ, U.K.
J Am Chem Soc. 2017 Mar 29;139(12):4362-4365. doi: 10.1021/jacs.7b01542. Epub 2017 Mar 20.
The catalytic use of a sodium amide has been exploited for formal allylic C(sp)-H bond activation of alkenes under mild conditions. Subsequent C-C bond formations with imines have proceeded in high yields with complete regioselectivity and excellent geometric selectivity. Aromatic cyano, chloro, and bromo functionalities are tolerated by the transition metal-free catalyst. Complex amines bearing a C═C double bond and distinct heteroaromatic units have been prepared in a single step. The critical importance of sodium versus other s-, p-, d-, and f-block metals as well as metal-free systems has been revealed. In addition, two catalytically active sodium-based intermediates were detected by NMR and HRMS analyses.
酰胺的催化作用已被用于在温和条件下实现烯烃的烯丙位 C(sp)-H 键的形式化亲电活化。随后与亚胺的 C-C 键形成反应以高收率、完全区域选择性和优异的立体选择性进行。无过渡金属催化剂可以容忍芳基氰基、氯基和溴基官能团。含有 C═C 双键和不同杂芳基单元的复杂胺可以一步制备得到。钠与其他 s、p、d 和 f 族金属以及无金属体系相比的关键重要性已经被揭示。此外，通过 NMR 和 HRMS 分析检测到了两种催化活性的基于钠的中间体。
