| Autor: |
Merad J; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Grant PS; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Stopka T; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Sabbatani J; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Meyrelles R; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria.; Institute of Theoretical Chemistry, University of Vienna, 1090 Vienna, Austria.; Doctoral School in Chemistry,University of Vienna, 1090 Vienna, Austria., Preinfalk A; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Matyasovsky J; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria., Maryasin B; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria.; Institute of Theoretical Chemistry, University of Vienna, 1090 Vienna, Austria., González L; Institute of Theoretical Chemistry, University of Vienna, 1090 Vienna, Austria., Maulide N; Institute of Organic Chemistry, University of Vienna, 1090 Vienna, Austria. |
| Abstrakt: |
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. |
