Mechanistic study on hydrogenation of enamides
||Mechanistic study on hydrogenation of enamides|
||SNIC Small Compute|
||Yangjianping Yang <firstname.lastname@example.org>|
||2020-09-15 – 2021-10-01|
We have developed an efficient hydrogenation of enamides catalyzed by N,P-Iridium complexes. Significantly, the hydrogenation of (E) and (Z) isomers converge to the same absolute configuration of the product. This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted enamides with excellent enantioselectivity, up to 99% ee. Deuterium and kinetic experiments suggest multiple pathways for the observed enantioconvergence: for α-aryl enamides a fast isomerization of the double bond can take place. on the other hand for α-alkyl enamides the double bond isomerization cannot be detected, rather a substrate chelation could prevail on steric hindrance effects. We are now exploring this reaction using DFT to explain the formation of the products.