Highly enantio-stereoselective Ni-catalyzed reductive cyclization to cyclopentanes with chiral quaternary centres of trisubstituted allylic siloxanes  

作　　者：Wanjun Chen Xinlong Yan Lin Fan Xu Guo Jian Yang Yiming Chen Shaofang Zhou Guodu Liu 

机构地区：[1]Inner Mongolia Key Laboratory of Fine Organic Synthesis,College of Chemistry and Chemical Engineering,Inner Mongolia University(South Campus),Hohhot 010030,China [2]Department of Chemistry,Baotou Teachers College,Baotou 014030,China [3]State Key Laboratory Breeding Base of Dao-di Herbs,National Resource Center for Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijng 100700,China

出　　处：《Green Synthesis and Catalysis》2024年第4期282-289,共8页绿色合成与催化（英文）

基　　金：financial support provided by the National Natural Science Foundation of China(No.22061032);Natural Science Foundation of Inner Mongolia(Nos.2020MS02022,and 2022QN02005);Science and Technology Program of Inner Mongolia(No.2020GG0134);Opening-fund from State Key Laboratory of Bio-organic and Natural Products Chemistry of SIOC(No.21300-5206002);“JUN-MA”Highlevel Talents Program of Inner Mongolia University(No.21300-5185121);“Grassland Talents”Program of Inner Mongolia(No.12000-12102414);High-level Recruit Program of Inner Mongolia(No.12000-13000603);Key Project at Central Government Level:the ability establishment of sustainable use for valuable Chinese medicine resources(No.2060302)is sincerely acknowledged。

摘　　要：The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.

关 键 词：All carbon 1 6-alkynone Ni-catalyzed reductive cyclization Stereoselective asymmetric catalysis Cyclopentane with chiral allylic quaternary stereocenter P-Chiral monophosphine ligand 

分 类 号：O62[理学—有机化学]