Illuminating anti-hydrozirconation: controlled geometric isomerization of an organometallic species.

ABSTRACT: A general strategy to enable the formal anti-hydrozirconation of arylacetylenes is reported that merges cis-hydrometallation using the Schwartz Reagent (Cp₂ZrHCl) with a subsequent light-mediated geometric isomerization at λ = 400 nm. Mechanistic delineation of the contra-thermodynamic isomerization step indicates that a minor reaction product functions as an efficient in situ generated photocatalyst. Coupling of the E-vinyl zirconium species with an alkyne unit generates a conjugated diene: this has been leveraged as a selective energy transfer catalyst to enable E → Z isomerization of an organometallic species. Through an Umpolung metal-halogen exchange process (Cl, Br, I), synthetically useful vinyl halides can be

SUBMITTER: Hostmann T 

PROVIDER: S-EPMC8356810 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature