Visible‐Light‐Enabled Direct Decarboxylative N‐Alkylation

Abstract

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.

Photocatalytic decarboxylative amidosulfonation enables direct transformation of carboxylic acids to sulfonamides

“…9 a Consistent with this conclusion, N -methylacridinium carboxylates do not undergo photoinduced decarboxylation, acridines do not catalyze photoinduced decarboxylation of carboxylate salts, and an addition of excess organic bases leads to suppression of the acridine-catalyzed decarboxylation. 9 In agreement with the prior observations, no decarboxylative amidosulfonation reaction was observed with the N -methyl 9-mesitylacridinium catalyst (Table S1 † ), and the involvement of alkyl and alkylsulfonyl radicals was supported by radical trapping and EPR spectroscopic experiments (Figures S1 and S2 † ). The experimental studies show that acridines A1–A3 are capable of catalyzing the direct amidosulfonation of carboxylic acids, while no reaction is observed with other common types of photocatalysts (Table S1 † ).…”

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

“…Photochemical decarboxylative aminations of aliphatic carboxylic acids were recently described by Larionov and colleagues [368] . The reaction is enabled by an acridine photocatalyst in combination with a Cu co‐catalyst using di‐ tert ‐butyl peroxide (DTBP) as the terminal oxidant (Scheme 85).…”

Direct decarboxylative Giese reactions

“…To address these issues, Larionov and co-workers recently devised a mild dual-catalytic system to facilitate the direct DGR of carboxylic acids without the need for pre-activation by deprotonation. 110 Employing their recently described new class of 9-arylacridine photocatalysts, 111 Acr-3 or Acr-4 were coupled with an efficient Cu( i )/Cu(0) catalytic cycle to access an impressive array of Giese adducts (Scheme 46A). Moderate to excellent yields were obtained for a variety of primary ( 120b , 81%), secondary ( 121 , 76%) and tertiary ( 120a, c–f , and 122 , 52–83%) carboxylic acids with good functional group tolerance for halogens and (un)saturated heterocycles.…”