Sur la thermocyclisation de cetones δ-ethyleniques en cyclohexanones

Development, Scope, and Mechanism of the Palladium-Catalyzed Intramolecular Hydroalkylation of 3-Butenyl β-Diketones

“…In contrast, a general and selective procedure for the addition of a stabilized carbon nucleophile to an unactivated olefin has not been identified. Hydroalkylation of γ-, δ-, ε-, or ζ-alkenyl alkyl ketones occurs thermally, but requires temperatures of ≥350 °C . Radical-mediated olefin hydroalkylation occurs under significantly milder conditions, but suffers from a number of problems including poor site- and product-selectivity and slow chain transfer. , The Lewis acid-catalyzed intramolecular hydroalkylation of alkenyl β-dicarbonyl compounds also occurs under mild conditions but suffers from limited generality and the problems associated with carbocationic intermediates …”

Palladium-Catalyzed Intramolecular Hydroalkylation of Unactivated Olefins with Dialkyl Ketones

“…The direct addition of the α-C−H bond of a dialkyl ketone across the CC bond of an unactivated olefin (hydroalkylation) is a transformation of considerable synthetic potential, but for which no effective procedure exists. For example, intramolecular hydroalkylation of γ-, δ-, ε-, or ζ-alkenyl alkyl ketones occurs thermally but requires temperatures of ≥350 °C . Radical-mediated olefin hydroalkylation occurs under relatively mild conditions but suffers from poor site selectivity for radical generation, poor product selectivity, and slow chain transfer .…”