Diastereodivergent Hydrosilylative Enyne Cyclization Catalyzed by N-Heterocyclic Carbene-Ni(o)  

作　　者：Meng Yu Xuefeng Yong Weiwei Gao Chun-Yu Ho 

机构地区：[1]Guangdong Province Key Laboratory of Catalysis,Department of Chemistry,Southern University of Science and Technology(SUSTech),1088 Xueyuon Avenue,Shenzhen,Guangdong 518055,China [2]Shenzhen Grubbs Institute,Deportment of Chemistry,Southern University of Science and Technology(SUSTech),1088 Xueyuan Avenue,Shenzhen,Guangdong 518055,China

出　　处：《Chinese Journal of Chemistry》2021年第6期1587-1592,共6页中国化学（英文版）

基　　金：the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002);NSFC(No.22071096);SUSTech(Nos.Y01501808 and Y01506014).

摘　　要：Catalytic diastereodivergent hydrosilylative enyne cyclization with high generality and broad scope was achieved using electronic ac-tivated N-heterocyclic carbene-Ni(O)as a catalyst and R_(3)SiH as silane(IPr^(Cl),syn-:anti-selectivity from up to 98:2 to 7:93 by Z=0,NH vs.NMs,R^(1)=n-pentyl).Heterocycles bearing homoallylsilane rather than vinylsilane was obtained chemoselectively.The undesired yet highly competitive reactivity was suppressed,like direct hydrosilylation of alkene and alkyne concurrently.Optionally,the homoallylsilane products could be reduced further in one-pot using IPr^(Me) as ligand and(EtO)_(3)SiH as silane under otherwise the same standard condition as the above,offering practical access to additional stereocenters and more diverse product structures from enynes.

关 键 词：N-Heterocyclic carbenes ENYNES Diastereodivergent synthesis HYDROSILYLATION Hydroalkenylation 

分 类 号：O62[理学—有机化学]