Open AccessDirect Stereodivergent Olefination of Carbonyl Compounds with Sulfur Ylides
Author(s) -
Jérémy Merad,
Phillip Grant,
Tobias Stopka,
Juliette Sabbatani,
Ricardo Meyrelles,
Alexander Preinfalk,
Ján Matyašovský,
Boris Maryasin,
Leticia González,
Nuno Maulide
Publication year - 2022
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.2c05637
Subject(s) - chemistry , reactivity (psychology) , sulfur , stereoselectivity , reagent , organic chemistry , substrate (aquarium) , scope (computer science) , combinatorial chemistry , catalysis , medicine , oceanography , alternative medicine , pathology , computer science , programming language , geology
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.