Nickel-Catalyzed Negishi Cross-Coupling of Alkyl Halides, Including Unactivated Tertiary Halides, with a Boron-Stabilized Organozinc Reagent

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.