Kinetics and Mechanism of Enantioselective Cu-Catalyzed Alcohol Silylation.

ABSTRACT: The enantioselective Cu-catalyzed dehydrogenative Si-O coupling of secondary benzylic alcohols with (nBu)₃SiH was investigated using a combination of in situ ¹H/¹⁹F NMR spectroscopic reaction monitoring, isotopic labeling, kinetic modeling, and computational studies. Macrokinetic behavior is governed by substrate-inhibited L*CuOR·ROH resting states: rates rise with conversion when [(nBu)₃SiH] > [ROH] and fall when [(nBu)₃SiH] < [ROH]. Alcohols bearing electron-withdrawing substituents are stronger inhibitors and show overall lower macrokinetic reactivity, but react faster than alcohols with electron-donating substituents in intermolecular competitions, indicating that inhibition is more substituent-sensitive than t

SUBMITTER: Helou de Oliveira PH 

PROVIDER: S-EPMC12679643 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature