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Catalyst‐Free Enantiospecific Olefination with In Situ Generated Organocerium Species
Author(s) -
Music Arif,
Hoarau Clément,
Hilgert Nicolas,
Zischka Florian,
Didier Dorian
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201810327
Subject(s) - cerium , reagent , pinacol , chemistry , aryl , catalysis , steric effects , in situ , electronegativity , functional group , boron , combinatorial chemistry , organic chemistry , alkyl , polymer
Abstract Described is the in situ formation of triorganocerium reagents and their application in catalyst‐free Zweifel olefinations. These unique cerium species were generated through novel exchange reactions of organohalides with n ‐Bu 3 Ce reagents. The adequate electronegativity of cerium allowed for compensating the disadvantages of both usually functional‐group‐sensitive organolithium species and less reactive organomagnesium reagents. Exchange reactions were performed on aryl and alkenyl bromides, enabling enantiospecific transformations of chiral boron pinacol esters. Finally, these new organocerium species were engaged in selective 1,2‐additions onto enolisable and sterically hindered ketones.