Catalyst-controlled vinylogous aza-MBH reactions of vinylcyclopentenone were performed, and it was found that the α-adducts were exclusively obtained by DABCO-catalysis, while the γ-adducts were the major products by DMAP-catalysis. We report here that the rate-determining step of the DABCO-catalyzed α-selective reactions is the Mannich-type C−C bond forming step, while that of the DMAP-catalyzed γ-selective reactions seems to be the β-elimination step.
- aza-Morita-Baylis-Hillman reaction
- kinetic isotope effect
- rate-determining step
ASJC Scopus subject areas
- Organic Chemistry