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Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (Z)-Alkenes.

ABSTRACT: A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and (Z)-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14-98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to be poor; however, the results disclosed herein remediate the previous findings. Control experiments were performed to investigate the different behavior of (Z)-alkenes and their more established (E)-counterparts.

SUBMITTER: Matviitsuk A

PROVIDER: S-EPMC9851372 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (<i>Z</i>)-Alkenes.

Matviitsuk Anastassia A Lee Panger Jesse J Denmark Scott E SE

ACS catalysis 20220607 12

A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and (<i>Z</i>)-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14-98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to b ...[more]

PMID: 36686398

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