Work

Additive-Controlled Regioswitching in Ni-Catalyzed Enantioselective Hydrophosphination of Unactivated Alkenes

Year: 2026

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Transition metal-catalyzed asymmetric hydrophosphination of unsaturated bonds offers the most direct route to chiral organophosphorus compounds. However, unactivated double bonds remain a longstanding challenge in this field due to their inherent low reactivity and the difficulty in achieving precise enantio- and regiocontrol. Herein, we report an amide-assisted asymmetric and regiodivergent hydrophosphination of unactivated alkenes catalyzed by a synergistic Ni(cod) 2 /BenzP and Brønsted acid system. Mechanistic studies and density functional theory calculations reveal that the weak noncovalent interactions between the amide substrate and the ligand are critical for selectivity. Diverging from conventional migratory insertion pathways, this strategy leverages distinct hydronickelation pathways mediated solely by pyridine-3-sulfonic acid or 3,5-difluorophenol additives, enabling precise control over enantioselectivity and regioselectivity. All of the branched and linear products are accessed with excellent regiodivergence, showcasing a versatile platform for the modular synthesis of chiral organophosphorus compounds.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c19022

Authors: Jian Zhou, Sichen Tao, Xinglong Zhang, Jun Wang

Institutions: Hong Kong Baptist University, Chinese University of Hong Kong

Language: English

Topic: Organophosphorus compounds synthesis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Hong Kong Baptist University, Research Grants Council, University Grants Committee, Chinese University of Hong Kong, Southern University of Science and Technology