The chiral pyridoxal-catalyzed biomimetic Mannich reaction: the mechanism and origin of stereoselectivity

Abstract

A biomimetic organocatalyst with a pyridoxal-like structure is one of the most successful examples of catalyzing organic reactions under mild conditions in an asymmetric synthesis field.

Elucidating the mechanism and origin of diastereoselectivity in scandium-catalyzed β-C(sp3)–H activation and transformation of an aliphatic aldimine

“…As part of our ongoing interest in organometallic catalysis, 5 we performed density functional theory (DFT) calculations to elucidate the mechanism and origin of regio- and diastereoselectivity in the Sc-catalyzed C(sp 3 )–H activation/[3 + 2] annulation of an aldimine with olefins. Density functional theory has been proved to be a powerful tool for exploring the mechanisms of organocatalytic 6 and organometallic reactions. 7 There is considerable interest in gaining an in-depth mechanistic understanding of substrate-controlled reversal of regioselectivity to facilitate the development of novel stereospecific and stereodivergent annulation reactions based on C–H activation mediated by rare-earth metals.…”

NHC-catalyzed enantioselective radical reactions of enal and pyridinium salt: mechanism and origin of regio- and stereoselectivities

“…In the present study, all computations were carried out using the Gaussian 16 program. 35 Due to the reliability of density functional theory in the mechanistic studies of organocatalytic reactions, [36][37][38][39][40][41][42][43] enzyme catalyzed reactions 44 and transition metal-catalyzed reactions, [45][46][47][48][49][50]…”

“…In the present study, all computations were carried out using the Gaussian 16 program. 35 Due to the reliability of density functional theory in the mechanistic studies of organocatalytic reactions, 36–43 enzyme catalyzed reactions 44 and transition metal-catalyzed reactions, 45–50 we have performed DFT calculations at the M06-2X (ref. 51 and 52)/6-311++G(d,p)/IEF-PCM HFB (ref.…”