Three-Component Asymmetric Ni-Catalyzed 1,2-Dicarbofunctionalization of Unactivated Alkenes via Stereoselective Migratory Insertion

Autor:	Omar Apolinar, Taeho Kang, Turki M. Alturaifi, Pranali G. Bedekar, Camille Z. Rubel, Joseph Derosa, Brittany B. Sanchez, Quynh Nguyen Wong, Emily J. Sturgell, Jason S. Chen, Steven R. Wisniewski, Peng Liu, Keary M. Engle
Rok vydání:	2022
Předmět:	Sulfonamides Colloid and Surface Chemistry Nickel Esters General Chemistry Alkenes Iodides Ligands Biochemistry Catalysis
Zdroj:	Journal of the American Chemical Society. 144:19337-19343
ISSN:	1520-5126 0002-7863
DOI:	10.1021/jacs.2c06636
Popis:	An asymmetric 1,2-dicarbofunctionalization of unactivated alkenes with aryl iodides and aryl/alkenylboronic esters under nickel/bioxazoline catalysis is disclosed. A wide array of aryl and alkenyl nucleophiles are tolerated, furnishing the products in good yield and with high enantioselectivity. In addition to terminal alkenes, 1,2-disubstituted internal alkenes participate in the reaction, establishing two contiguous stereocenters with high diastereoselectivity and moderate enantioselectivity. A combination of experimental and computational techniques shed light on the mechanism of the catalytic transformation, pointing to a closed-shell pathway with an enantiodetermining migratory insertion step, where stereoinduction arises from synergistic interactions between the sterically bulky achiral sulfonamide directing group and the hemilabile bidentate ligand.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::cbc04eb38fa738ca40629274494874ee https://doi.org/10.1021/jacs.2c06636 Zobrazit plný text záznamu