The development of efficient and selective C À N bond-forming reactions from abundant feedstock chemicals remains acentral theme in organic chemistry owing to the key roles of amines in synthesis,d rug discovery,a nd materials science.H erein, we present ad ual catalytic system for the Nalkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids,by-passing their preactivation as redox-active esters.The reaction, which is enabled by visible-light-driven, acridine-catalyzed decarboxylation, provides access to N-alkylated secondary and tertiary anilines and N-heterocycles.Additional examples,including double alkylation, the installation of metabolically robust deuterated methyl groups,a nd tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation( DDA) reaction.
Carboxylic acids can now serve as a single point of entry to several sulfonyl functional groups by a one-step organophotocatalytic sulfonylation, revealing structural effects that enable the photocatalysis.
Sulfonamides are now accessible directly from carboxylic acids by a one-step, tricomponent decarboxylative amidosulfonation that provides the missing link between the two key functionalities.
Conjugate addition
is one of the most synthetically useful carbon–carbon bond-forming
reactions; however, reactive carbon nucleophiles are typically required
to effect the addition. Radical conjugate addition provides an avenue
for replacing reactive nucleophiles with convenient radical precursors.
Carboxylic acids can serve as simple and stable radical precursors
by way of decarboxylation, but activation to reactive esters is typically
necessary to facilitate the challenging decarboxylation. Here, we
report a direct, dual-catalytic decarboxylative radical conjugate
addition of a wide range of carboxylic acids that does not require
acid preactivation and is enabled by the visible light-driven acridine
photocatalysis interfaced with an efficient copper catalytic cycle.
Mechanistic and computational studies provide insights into the roles
of the ligands and metal species in the dual-catalytic process and
the photocatalytic activity of substituted acridines.
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