Abstract
The direct synthesis of ketones via carbon–carbon bond formation represents one of the most important challenges in organic synthesis. Hydroacylation of alkenes offers perhaps the most efficient and atom-economical approach for the preparation of ketones employing carbonyl compounds and alkenes as feedstocks. State-of-the-art hydroacylation is typically achieved by a transition metal-catalysed coupling of an aldehyde and an alkene but is plagued by competing decarbonylation, requiring the installation of directing groups in the aldehyde reactant. Herein, we present a method for the hydroacylation of alkenes employing amides in a metal-free regime, proceeding by a new mechanism and offering orthogonal reactivity to the conventional, metal-catalysed alternatives.
Highlights
The direct synthesis of ketones via carbon–carbon bond formation represents one of the most important challenges in organic synthesis
Ketones and aldehydes are perhaps the quintessential functional groups of organic chemistry. Their unique ability to mediate C–C bond forming reactions serving as either electrophiles or nucleophiles remains one of the cornerstones of the past 4 decades of organic synthesis
The presented approach to olefin hydroacylation is a method whereby ketone synthesis can be achieved by the direct, metal-free coupling of secondary amides and alkenes
Summary
The direct synthesis of ketones via carbon–carbon bond formation represents one of the most important challenges in organic synthesis. While intramolecular olefin hydroacylation has reached high levels of efficiency and selectivity, intermolecular hydroacylation still typically relies on (a) aldehydes equipped with directing groups designed to minimize decarbonylation as well as on (b) activated alkene partners Aiming to address these challenges and guided by previous work on amide activation[5,15,16,17,18,19], we report an approach to olefin hydroacylation relying on an intermolecular coupling of secondary amides and alkenes (Fig. 1d), which requires neither a transition metal catalyst nor directing groups and which delivers ketones with high levels of chemo- and regioselectivity
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