Year: 2024
Type: article
Abstract: α‐substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in natural products and pharmaceuticals. We report the α‐acetylation of C(sp 3 )−H substrates R−H with arylmethyl ketones ArC(O)Me to provide α‐alkylated ketones ArC(O)CH 2 R at RT with t BuOO t Bu as oxidant via copper(I) ‐diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α‐substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu II ](CH 2 C(O)Ar) that capture alkyl radicals R• to give R−CH 2 C(O)Ar outcompeting dimerization of the copper(II) enolate to give the 1,4‐diketone ArC(O)CH 2 CH 2 C(O)Ar.
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
Awards: SusChEM: C-H Functionalization with Earth Abundant Metals, G1144718286, G1274588918, CAS: Catalytic sp3 Carbon-Hydrogen (C-H) Functionalization with Earth Abundant Metals, IMPROVED MODELING OF TRANSITION METAL MATERIALS. APPLICATIONS TO CATALYSIS AND TECHNETIUM CHEMISTRY, G1995909496, G222768804, G26343026, G3093119397, MODELING OF CATALYTIC PROCESSES FOR MORE EFFICIENT UTILIZATION OF HYDROCARBON RESOURCES, G5648016710, CAS: Catalytic sp3 Carbon-Hydrogen (C-H) Functionalization with Earth Abundant Metals, MRI: Acquisition of a Computer Cluster for the Computational Chemistry Program at the University of North Texas, G7493551856, G8021868591, G8384479287
OpenAlex ID: W4403902600