ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6728 - 6739

Опубликована: Апрель 16, 2024

In the presence of Pd(Xantphos) and an electron-deficient arylboronic acid cocatalyst, azoles such as pyrazoles, triazoles, tetrazoles, purines undergo regioselective, dehydrative allylations with allylic alcohols. The boronic has a significant effect on both rate regioselectivity these reactions. Herein, combined experimental computational mechanistic study synergistic organoboron- palladium-catalyzed allylation is described. Kinetic analysis evaluation effects substitution reaction point toward turnover-limiting ionization alcohol, Lewis activation by acid. Computational modeling pathway density functional theory indicates that alcohol also regioselectivity-determining step resulting ion pair undergoes C–N bond formation through outer-sphere mechanism. An unexpected observation autocatalysis emerged from kinetic motivated additives, leading to development improved protocol.

Язык: Английский