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Direct Stereodivergent Olefination of Carbonyl Compounds with Sulfur Ylides.

ABSTRACT: The reactivity of phosphorus and sulfur ylides toward carbonyl compounds constitutes a well-known dichotomy that is a common educational device in organic chemistry─the former gives olefins, while the latter gives epoxides. Herein, we report a stereodivergent carbonyl olefination that challenges this dichotomy, showcasing thiouronium ylides as valuable olefination reagents. With this method, aldehydes are converted to Z-alkenes with high stereoselectivity and broad substrate scope, while N-tosylimines provide a similarly proficient entry to E-alkenes. In-depth computational and experimental studies clarified the mechanistic details of this unusual reactivity.

SUBMITTER: Merad J

PROVIDER: S-EPMC9284548 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Direct Stereodivergent Olefination of Carbonyl Compounds with Sulfur Ylides.

Merad Jérémy J Grant Phillip S PS Stopka Tobias T Sabbatani Juliette J Meyrelles Ricardo R Preinfalk Alexander A Matyasovsky Ján J Maryasin Boris B González Leticia L Maulide Nuno N

Journal of the American Chemical Society 20220630 27

The reactivity of phosphorus and sulfur ylides toward carbonyl compounds constitutes a well-known dichotomy that is a common educational device in organic chemistry─the former gives olefins, while the latter gives epoxides. Herein, we report a stereodivergent carbonyl olefination that challenges this dichotomy, showcasing thiouronium ylides as valuable olefination reagents. With this method, aldehydes are converted to <i>Z</i>-alkenes with high stereoselectivity and broad substrate scope, while ...[more]

PMID: 35770382

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