Synergy of activating substrate and introducing C–H…O interaction to achieve Rh2(II)-catalyzed asymmetric cycloisomerization of 1,n-enynes

作     者：Rui Wu Kai Chen Jun Ma Zhi-Xiang Yu Shifa Zhu Rui Wu;Kai Chen;Jun Ma;Zhi-Xiang Yu;Shifa Zhu

作者机构：Key Lab of Functional Molecular Engineering of Guangdong ProvinceSchool of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhou 510640China College of Chemistry and Chemical EngineeringCentral South UniversityChangsha 410083China Beijing National Laboratory for Molecular Sciences(BNLMS)Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of EducationCollege of ChemistryPeking UniversityBeijing 100871China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2020年第63卷第9期

页      面：1230-1239页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070304[理学-物理化学(含∶化学物理)] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：the National Natural Science Foundation of China(21871096 21672071 91856105) the Ministry of Science and Technology of China(2016YFA0602900) the Natural Science Foundation of Guangdong(2018B030308007 2018A030310359 2016A030310433) the Science and Technology Program of Guangzhou(201707010316) the Fundamental Research Funds for the Central Universities South China University of Technology 

主　　题：asymmetric cycloisomerization chiral cyclopropane dirhodium catalysis carbene 

摘      要：We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild *** activated group,CHZ(Z is electronwithdrawing group(EWG)),in the enyne substrates exerts two synergetic roles,one is to activate alkyne for the cyclopropanation reaction;the other is to introduce the C–H…O interaction between substrate and catalyst(reducing the energy barrier of the reaction).This double-mode activation was supported by both density functional theory(DFT)calculations and experimental *** strategy was also extended to other CH2 Z(Z can be OH,OMe,F)as activating groups that made the CH2 more acidic so that the substrates could also form increased C–H…O interaction with the catalyst.