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

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

机构地区:[1]Key Lab of Functional Molecular Engineering of Guangdong Province,School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,China [2]College of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China [3]Beijing National Laboratory for Molecular Sciences(BNLMS),Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,College of Chemistry,Peking University,Beijing 100871,China

出  处:《Science China Chemistry》2020年第9期1230-1239,共10页中国科学(化学英文版)

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。

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 conditions.The 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 tests.This 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.

关 键 词:asymmetric cycloisomerization chiral cyclopropane dirhodium catalysis CARBENE 

分 类 号:O621.251[理学—有机化学] O641.3[理学—化学]

 

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