Pd/Zn Dual Catalysis for Site-,Enantio-,and Diastereo-Divergent 2-(Alkoxycarbonyl)allylation ofα-Hydroxyketones with Morita–Baylis–Hillman Adducts  

作　　者：Yong Liu Chaopeng Li Rui Zhang Zibo Liu Zhaobin Han Zheng Wang Kuiling Ding 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032 [2]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210 [3]Frontiers Science Center for Transformative Molecules,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2024年第10期2607-2618,共12页中国化学会会刊（英文）

基　　金：the National Key R&D Program of China(grant nos.2023YFA1506700,2022YFA1503702,and 2021YFF0701602);National Natural Science Foundation of China(NSFC,grant nos.22231011 and 22271303);Shanghai Scientific and Technological Innovation Project,China(grant no.22JC1401000).

摘　　要：A synergistic Pd/Zn dual chiral catalyst system has been developed for the stereodivergent transformation of Morita–Baylis–Hillman(MBH)carbonates and unprotectedα-hydroxyketones to afford the corresponding allylation products(>50 examples).These products bearing vicinal stereocenters were obtained in high yields with excellent regio-/diastereo-/enantioselectivities.On cyclization in an acidic medium,the allylation products could transform to the corresponding acyl-functionalizedβ,γ-disubstitutedα-methylene-γ-butyrolactones(AMGBLs).All four stereoisomers of AMGBL were readily accessed using the same starting materials with full control of the stereochemistry of the contiguous stereogenic centers,simply by switching the chiral ligand combination for the Pd/Zn system.A nucleophilic site-divergent reactivity was observed for the allylation of primary and secondaryα-hydroxyketones,suggesting that distinct enolate intermediates might have prevailed in these reactions.

关 键 词：asymmetric catalysis Pd/Zn dual catalyst 2-(alkoxycarbonyl)allylation stereodivergent sitedivergent 

分 类 号：O62[理学—有机化学]