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Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines

Vivek Aryal, Lucas J. Chesley, Doleshwar Niroula, Rishi R. Sapkota, Roshan K. Dhungana, Ramesh Giri

2022ACS Catalysis31 citationsDOIOpen Access PDF

Abstract

We disclose a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ-alkenylketimines with aryl halides and alkylzinc reagents. The reaction produces γ-C(sp3)-branched δ-arylketones with the construction of two C(sp3)–C(sp3) and C(sp3)–C(sp2) bonds. Electron-deficient alkenes play crucial dual roles as ligands to stabilize reaction intermediates and to increase catalytic rates for the formation of C(sp3)–C(sp3) bonds. This alkene alkylarylation reaction is also effective for secondary alkylzinc reagents and internal alkenes and proceeds with a complete regio- and stereocontrol, affording products with up to three contiguous all-carbon all-cis secondary stereocenters.

Topics & Concepts

StereocenterAlkeneChemistryCatalysisReagentStereoselectivityArylVicinalMedicinal chemistryRegioselectivityStereochemistryCombinatorial chemistryOrganic chemistryEnantioselective synthesisAlkylCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsCyclopropane Reaction Mechanisms
Ni-Catalyzed Regio- and Stereoselective Alkylarylation of Unactivated Alkenes in γ,δ-Alkenylketimines | Litcius