Jiang Ling-Feng, Wu Shao-Hua, Jiang Yu-Xuan, Ma Hong-Xiang, He Jia-Jun, Bi Yang-Bo, Kong De-Yi, Cheng Yi-Fei, Cheng Xuan, Deng Qing-Hai
The Education Ministry Key Laboratory of Resource Chemistry, Joint International Research Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, and Shanghai Frontiers Science Center of Biomimetic Catalysis, Shanghai Normal University, 200234, Shanghai, China.
Nat Commun. 2024 Jun 10;15(1):4919. doi: 10.1038/s41467-024-49313-x.
Chiral 1,2,3-triazoles are highly attractive motifs in various fields. However, achieving catalytic asymmetric click reactions of azides and alkynes for chiral triazole synthesis remains a significant challenge, mainly due to the limited catalytic systems and substrate scope. Herein, we report an enantioselective azidation/click cascade reaction of N-propargyl-β-ketoamides with a readily available and potent azido transfer reagent via copper catalysis, which affords a variety of chiral 1,2,3-triazoles with up to 99% yield and 95% ee under mild conditions. Notably, chiral 1,5-disubstituted triazoles that have not been accessed by previous asymmetric click reactions are also prepared with good functional group tolerance.
手性1,2,3-三唑在各个领域都是极具吸引力的结构单元。然而，实现用于手性三唑合成的叠氮化物和炔烃的催化不对称点击反应仍然是一项重大挑战，主要原因是催化体系和底物范围有限。在此，我们报道了通过铜催化，N-炔丙基-β-酮酰胺与一种易于获得且有效的叠氮转移试剂发生对映选择性叠氮化/点击串联反应，该反应在温和条件下可提供多种手性1,2,3-三唑，产率高达99%，对映体过量值高达95%。值得注意的是，之前的不对称点击反应无法得到的手性1,5-二取代三唑也能以良好的官能团耐受性制备出来。
