Li Xiaoning, Chen Zunsheng, Liu Yan, Luo Nianhua, Chen Weiming, Liu Chenfu, Yu Fuchao, Huang Jiuzhong
School of Pharmacy, Gannan Medical University, Ganzhou 341000, PR China.
Key Laboratory of Prevention and Treatment of Cardiovascular and Cerebrovascular Diseases of Ministry of Education, Gannan Medical University, Ganzhou 341000, PR China.
J Org Chem. 2022 Aug 5;87(15):10349-10358. doi: 10.1021/acs.joc.2c00096. Epub 2022 Jul 27.
The cleavage and transformation of alkenyl C(sp)-N bonds is a significant synthetic challenge. Herein we described an unprecedented nickel-catalyzed reductive borylation of enaminones to synthesize β-ketone boronic esters. Notably, Bpin played the dual role in this process, and water served as a hydrogen source, which was transferred to target products. The air-stable nickel catalyst was applied to the cleavage of alkenyl C(sp)-N bonds, concomitant with the reductive process of the alkenyl boronic ester intermediates, on the basis of the mechanism study.
烯基C(sp)-N键的裂解和转化是一项重大的合成挑战。在此，我们描述了一种前所未有的镍催化烯胺酮的还原硼化反应，用于合成β-酮硼酸酯。值得注意的是，Bpin在这一过程中发挥了双重作用，水作为氢源，被转移到目标产物中。基于机理研究，空气稳定的镍催化剂被用于烯基C(sp)-N键的裂解，同时伴随着烯基硼酸酯中间体的还原过程。
