Abstract
<p>Herein, we present a new concept for the hydroacylation of alkenes employing amides in a metal-free regime, proceeding by an entirely new mechanism and offering orthogonal reactivity to the conventional, metal-catalysed alternatives. </p>
Highlights
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
An overabundance of ketone syntheses rely on the direct, one-step 1,2-addition of organometallic reagents to suitable electrophilic carboxylic acid derivatives.[1,2]. These nucleophilic substitutions can suffer from a number of limitations including overaddition, poor chemoselectivity regarding the presence of other carbonyl groups, excessive use of acylating reagents or tedious procedures
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
Summary
Ketones and aldehydes are perhaps the quintessential functional groups of organic chemistry. State-of-the-art hydroacylation is typically achieved by a transition metal-catalyzed coupling of an aldehyde and an alkene but is plagued by competing decarbonylation, requiring the installation of directing groups in the aldehyde reactant.
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