Iron-Catalyzed Gamma-Gamma Dimerization of Siloxydienes.

Autor: Galaktionova D; Department of Chemistry, University of Illinois-Chicago, 845 West Taylor St, Chicago, IL 60607, USA., Liu X; Department of Chemistry, University of Illinois-Chicago, 845 West Taylor St, Chicago, IL 60607, USA., Chen X; Department of Chemistry, University of Illinois-Chicago, 845 West Taylor St, Chicago, IL 60607, USA., Mohr JT; Department of Chemistry, University of Illinois-Chicago, 845 West Taylor St, Chicago, IL 60607, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 22; Vol. 30 (5), pp. e202302901. Date of Electronic Publication: 2023 Dec 04.
DOI: 10.1002/chem.202302901
Abstrakt: We report the oxidative dimerization reaction of siloxydienes derived from simple enones that creates a new gamma-gamma (γ-γ) C-C bond using catalytic iron and benzoyl peroxide as the terminal oxidant in acetonitrile solvent at ambient temperature. The reaction shows a broad substrate scope including cyclic and acyclic siloxydienes derived from ketones, aldehydes, and esters, which are converted to 1,8-dicarbonyl compounds under mild catalytic reaction conditions in 19-89 % yield across 30 examples. The method is suitable for the coupling of sterically demanding carbon centers, including the formation of vicinal quaternary centers. Conceptually, the dienol ether serves as a precursor to a conjugated radical cation, which undergoes highly site selective γ-dimerization reactions. The γ-γ dimerization strategy is applied to the synthesis of a bioactive analogue of honokiol.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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