Understanding the Mechanism of Diels-Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]^- (E = P, As; X = O, S, Se) Anions.

ABSTRACT: While Diels-Alder (DA) reactions involving neutral or cationic dienophiles are well-known, the characteristics of the analogous reactions with anionic dienophiles are practically unexplored. Herein we present the first comparative computational investigations on the characteristics of DA cycloadditions with anionic dienophiles on the basis of the reactions of [ECX]^- anions (E = P, As; X = O, S, Se) with 2H-pyran-2-one. All of these reactions were found to be both kinetically and thermodynamically feasible, enabling synthetic access toward 2-phosphaphenolate and arsaphenolate derivatives in the future. This study also reveals that the [ECO]^- anions show clear regioselectivity, while for [ECS]^- and [ECSe]^- anions, the two possible reaction c

SUBMITTER: Horvath A 

PROVIDER: S-EPMC9131451 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature