A Change in C-H Activation Mechanism: Experimental and Computational Investigations of Rh-Catalyzed Disubstituted Benzene Functionalization.

ABSTRACT: We report the ethenylation of 1,3- and 1,2-disubstituted benzenes using [(η²-C₂H₄)₂Rh-(μ-OAc)]₂ as a catalyst precursor and Cu-(OPiv)₂ as the oxidant. The regioselectivity of alkenylation for 1,3-disubstituted benzenes produces 3,5-disubstituted styrene products, while the alkenylation of 1,2-disubstituted benzenes produces 3,4-disubstituted styrene products. The rate of alkenylation is influenced by steric and electronic factors based on the substituents of the benzene unit. In all cases, 1,2-disubstituted benzenes react faster than 1,3-disubstituted benzenes, with a rate difference that is from 2 times up to >70 times more rapid for 1,2-disubstituted substrates. This is likely due to the difference in the number of accessi

SUBMITTER: Reid CW 

PROVIDER: S-EPMC12606707 | biostudies-literature | 2025 Nov

REPOSITORIES: biostudies-literature