Chemodivergent,enantio-and regioselective couplings of alkynes,aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis  

发散式镍催化醛、炔和硅烷的区域和对映选择性偶联反应

作　　者：Jia-Ming Liu Xuexiang Ma Guang Chen Wang Wan Zhiyang Li Youjun Xu Dongju Zhang Shi-Liang Shi 刘佳明;马雪香;陈光;万旺;李知阳;许佑君;张冬菊;施世良

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China [2]Key Lab of Colloid and Interface Chemistry,Ministry of Education,Institute of Theoretical Chemistry,School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,China [3]School of Pharmaceutical Engineering,Shenyang Pharmaceutical University,Shenyang 110016,China

出　　处：《Science Bulletin》2025年第5期674-682,共9页科学通报(英文版)

基　　金：National Key R&D Program of China(2021YFF0701600 and 2022YFA1503702);National Natural Science Foundation of China(22325110,92256303,21821002,and 22171280);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000);Ningbo Natural Science Foundation(2022j017);Program of Shanghai Academic/Technology Research Leader(22XD1424900);CAS Youth Interdisciplinary Team(JCTD-2021-11).

摘　　要：Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal.We here describe chemodivergent,highly enantio-and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes,aldehydes,and silanes.A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products(silyl-protected trisubstituted chiral allylic alcohols,oxasilacyclopentenes,and silicon-stereogenic oxasilacyclopentenes)in a single chemical operation.The use of a bulky C2-symmetric N-heterocyclic carbene(NHC)ligand for nickel catalyst is the key to enable simultaneous exceptional control of stereo-and regioselectivity(up to 99%enantiomeric excess(ee),>99:1 regiomeric ratio(rr),>99:1 E/Z)and high efficiency(up to 99%yield).Computational studies elucidate the origin of chemodivergency and reveal the critical role of NHC in the enantioselectivity-and rate-determining oxidative cyclization step via anη2-aldehydeη2-alkyne Ni five-centered transition state.We expected that the enantioselectiveη2-activation mode be widely applicable in other Ni-catalyzed carbonyl couplings.

关 键 词：Asymmetric catalysis Divergent synthesis Nickel catalysis Reductive coupling Carbonyl addition Multicomponent reaction 

分 类 号：O62[理学—有机化学]