Boron-Mediated Hydroalkylation of Unactivated Olefins: An Anti -Markovnikov Approach to Congested Carbon Centers
Year: 2026
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Transition metal-catalyzed hydroalkylations offer efficient routes to install alkyl fragments onto readily available olefins. However, the formation of quaternary carbon centers through olefin hydroalkylations with tertiary alkyl electrophiles remains a formidable synthetic challenge. Difficulty arises as a result of steric congestion, which slows the rate of oxidative addition and promotes deleterious β-hydride elimination. Here, we report a boron-mediated coupling strategy using nickel/photoredox dual catalysis that circumvents these limitations and enables anti -Markovnikov hydroalkylations of unactivated olefins with carboxylic acid derivatives as alkylating partners. Our protocol proceeds via initial hydroboration, followed by a sequence of deboronative and decarboxylative radical generation, radical sorting, and bimolecular homolytic substitution (S H 2). This mild and practical approach allows the construction of densely substituted carbon frameworks, including sterically congested quaternary carbon centers, providing a solution to a long-standing challenge in fragment-coupling chemistry.
DOI: 10.1021/jacs.6c01091
Institution: University of Bristol
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7135227757