Abstract
•Atroposelective hydrophosphination of internal alkynes •Construction of axial and P-chirality •Broad reaction scope, including symmetrical and nonsymmetrical secondary phosphines •Excellent regioselectivity, E-selectivity, enantioselectivity, and diastereoselectivity Palladium-catalyzed underexplored atroposelective hydrophosphination of sterically hindered internal alkynes with secondary phosphines has been realized, affording C-N axially chiral trisubstituted olefins (vinylphosphines) in excellent regioselectivity, (E)-selectivity, and enantioselectivity. The axial chirality was constructed via the integration of hydrophosphination and dynamic kinetic transformation of the alkynes, with both symmetrical and nonsymmetrical secondary phosphines being applicable. Palladium-catalyzed underexplored atroposelective hydrophosphination of sterically hindered internal alkynes with secondary phosphines has been realized, affording C-N axially chiral trisubstituted olefins (vinylphosphines) in excellent regioselectivity, (E)-selectivity, and enantioselectivity. The axial chirality was constructed via the integration of hydrophosphination and dynamic kinetic transformation of the alkynes, with both symmetrical and nonsymmetrical secondary phosphines being applicable.
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