Stereodivergent Pd/Cu Catalysis for Asymmetric Desymmetric Alkylation of Allylic Geminal Dicarboxylates  

作　　者：Xiaohong Huo Ling Zhao Yicong Luo Yue Wu Yuwen Sun Guanlin Li Tatiana Gridneva Jiacheng Zhang Yong Ye Wanbin Zhang 

机构地区：[1]Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,Frontiers Science Center for Transformative Molecules,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240 [2]College of Chemistry,Zhengzhou University,Zhengzhou 450052

出　　处：《CCS Chemistry》2022年第5期1720-1731,共12页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(nos.21620102003,21831005,21901158,and 21991112);the Shanghai Sailing Program(no.19YF1421900);Shanghai Municipal Education Commission(no.201701070002E00030);National Key R&D Program of China(no.2018YFE0126800);the Science and Technology Commission of Shanghai Municipality(no.19JC1430100);Zhiyuan Scholar Program(no.ZIRC2020-04).

摘　　要：AstereodivergentPd/Cucatalyst systemforasymmetric desymmetric alkylation of allylic geminal dicarboxylates has been developed,which was successfully applied to the asymmetric synthesis of β-hydroxycarbonylmotifs bearing a versatile carbon-carbon double bond in an enantio-and diastereodivergent manner.A wide scope of substrates including challenging alkylsubstituted,2-substituted,and3,3′-disubstitutedallylic species are compatible with this catalytic system,delivering the substituted products in high to excellent yieldsandwith excellent diastereo-(upto>20:1 dr)and enantioselectivities(up to>99%ee).Furthermore,the mechanism of this dual Pd/Cu catalytic system including:(1)the desymmetrization process ofgeminal dicarboxylates;(2)the origin of regioselectivity(branched or linear);(3)the enantio-and diastereoselectivity observed by changing the combinations of two chiral metal catalysts,have been carefully investigated by theoretical calculations.

关 键 词：stereodivergent synthesis bimetallic catalysis DESYMMETRIZATION Pd/Cu dual catalysis asymmetric allylic substitution 

分 类 号：O62[理学—有机化学]