title: Isomerization of Olefins Triggered by Rhodium-Catalyzed C-H Bond Activation: Control of Endocyclic β-Hydrogen Elimination.
abstract: Five-membered metallacycles are typically reluctant to undergo endocyclic β-hydrogen elimination. The rhodium-catalyzed isomerization of 4-pentenals into 3-pentenals occurs through this elementary step and cleavage of two C-H bonds, as supported by deuterium-labeling studies. The reaction proceeds without decarbonylation, leads to trans olefins exclusively, and tolerates other olefins normally prone to isomerization. Endocyclic β-hydrogen elimination can also be controlled in an enantiodivergent reaction on a racemic mixture.
authors.affiliation: Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD (UK).
authors.forename: Stephanie Y Y
authors.initials: SY
authors.lastname: Yip
authors.affiliation: Department of Chemistry, University of Liverpool, Crown Street, L69 7ZD (UK). aissa@liverpool.ac.uk.
authors.forename: Christophe
authors.initials: C
authors.lastname: Aïssa
keywords: CH activation; isomerization; metallacycles; rhodium; β-H elimination