Abstract
Recently, transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. However, all these reactions rely on facially selective arylmetalation of the pendant olefinic unit. Here, we successfully apply acylnickelation as the enantiodetermining step in the asymmetric nickel-catalyzed reductive carbo-acylation of aryl carbamic chloride-tethered alkenes with primary and secondary alkyl iodides as well as benzyl chlorides as the coupling partners, using manganese as a reducing agent. By circumventing the use of pre-generated organometallics, this reductive strategy enables the synthesis of diverse enantioenriched oxindoles bearing a quaternary stereogenic center under mild reaction conditions with high tolerance of a broad range of functional moieties.
Highlights
Transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles
Transition-metal-catalyzed dicarbofunctionalization consisting of a cyclization/cross-coupling cascade provides a powerful method to access various benzene-fused cyclic compounds starting from tethered alkenes[1,2,3,4,5,6,7,8,9,10,11,12,13]
Reductive dicarbofunctionalization represents a step-economical approach with high functionality tolerance through circumventing the use of organometallics as the coupling partner, and gains growing interest from organic chemists[14,15,16,17,18,19,20,21,22,23,24]
Summary
Transition-metal-catalyzed asymmetric dicarbofunctionalization of tethered alkenes has emerged as a powerful method for construction of chiral cyclic carbo- and heterocycles. We report a Ni-catalyzed asymmetric reductive carboacylation of aryl carbamic acid chloride-tethered alkenes with alkyl halides as the coupling partner, in which the intramolecular acylnickelation serves as the enantiodetermining step, to construct the oxindole motif bearing a challenging quaternary stereocenter featured in numerous biologically active compounds[41] (Fig. 1c).
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