摘要
Dirhodium(Ⅱ)complexes have achieved great success in organic synthesis,and fine-tuning their catalytic properties with various bridging ligands is well-investigated in carbene chemistry.However,combining dirhodium(Ⅱ)with a sophisticated ligand as a catalyst in other reactions is still extremely challenging,especially for the asymmetric synthesis of valuable chiral molecules.Herein,we report a dirhodium(Ⅱ)/(S)-Me O-BIPHEP catalytic system for the challenging asymmetricβ-alkenylation ofα,β-unsaturated aldehydes,affording the corresponding chiral conjugate addition products in good yields with high enantioselectivities.A couple of drug-derived substrates were also compatible with the protocol,which has been successfully used to prepare biologically relevant pyranochromene compounds.Preliminary mechanistic studies suggested that the dirhodium core might remain intact over the catalytic cycle,and the chiral diphosphine ligand plays a key role in this novel reactivity and determining the high enantioselectivities of the asymmetric conjugate addition.
基金
supported by the National Key R&D Program of China(2021YFA1500100)
the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000,XDB1180000)
the National Natural Science Foundation of China(92256303,22171278,21821002)
the Shanghai Science and Technology Committee(23ZR1482400)
the Natural Science Foundation of Ningbo(2023J034)
the Postdoctoral Fellowship Program of China Postdoctoral Science Foudation(GZC20232863)
the China Postdoctoral Science Foundation(2024M763426)
the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University
the Research Funds of Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences。
