Nickel^II-catalyzed asymmetric photoenolization/Mannich reaction of (2-alkylphenyl) ketones.

ABSTRACT: A diastereo- and enantioselective photoenolization/Mannich (PEM) reaction of ortho-alkyl aromatic ketones with benzosulfonimides was established by utilizing a chiral N,N'-dioxide/Ni(OTf)₂ complex as the Lewis acid catalyst. It afforded a series of benzosulfonamides and the corresponding ring-closure products, and a reversal of diastereoselectivity was observed through epimerization of the benzosulfonamide products under continuous irradiation. On the basis of the control experiments, the role of the additive LiNTf₂ in achieving high stereoselectivity was elucidated. This PEM reaction was proposed to undergo a direct nucleophilic addition mechanism rather than a hetero-Diels-Alder/ring-opening sequence. A possible transition state model with a pho

SUBMITTER: Yang L 

PROVIDER: S-EPMC9337722 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature