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Asymmetric alkyl-alkyl coupling between electron-deficient and unactivated alkenes to access α-chiral phosphines by
Jian-Yu Zou1,2, Fang-Li Xing1, Quan-Xing Zi1
1Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Shenzhen Grubbs Institute, Guangming Advanced Research Institute, Department of Chemistry, and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, P. R. China.
Abstract:
α-Chiral phosphorus compounds have broad applications as organic catalysts or ligands in organic chemistry and related areas. Herein, we disclose a Ni-catalyzed enantioselective cross-hydrodimerization of alkenyl phosphine sulfides with unactivated alkenes to access α-chiral phosphine sulfides, representing the first example of asymmetric hydrodimerization of electron-deficient alkenes with electron-rich alkenes. Key to success is the precise recognition between electron-deficient alkenes and electron-rich alkenes and streamlined alkyl-alkyl bond forming with the control of chemo-, regio-, and enantioselectivity. This strategy requires alkenes as sole precursors for asymmetric alkyl-alkyl cross-coupling, circumventing the use of stoichiometric amounts of alkyl electrophiles or alkyl nucleophiles as coupling partners. The mild conditions tolerate a wide range of functional groups, providing direct access to α-chiral phosphines through a carbon-carbon bond-forming process without prefunctionalized coupling precursors.
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