ABSTRACT
Nickel-catalyzed cross-coupling of unactivated tertiary alkyl electrophiles with alkylmetal reagents is still a challenge. We report herein a nickel-catalyzed Negishi cross-coupling of alkyl halides, including unactivated tertiary halides, with boron-stabilized organozinc reagent BpinCH2ZnI, yielding versatile organoboron products with high functional-group tolerance. Importantly, the Bpin group was found to be indispensable for accessing the quaternary carbon center. The synthetic practicability of the prepared quaternary organoboronates was demonstrated by their conversion to other useful compounds.
ABSTRACT
An iridium-catalyzed enantioconvergent coupling of the versatile boron-stabilized organozinc reagent BpinCH2ZnI with a racemic branched allylic carbonate has been developed here, which differs from our previous work by using 1,1-bisborylmethane through the kinetic resolution process. The reaction has a broad substrate scope, and various chiral homoallylic organoboronic esters could be obtained in good yields with excellent enantioselectivities. The synthetic practicability of the products was demonstrated by their conversion to other useful families of compounds.
