Direct decarboxylative Giese amidations: photocatalytic <i>vs.</i> metal- and light-free

Kitcatt, David M.; Scott, Katie A.; Rongione, Elena; Nicolle, Simon; Lee, Ai-Lan

doi:10.1039/d3sc03143h

Cited by 14 publications

(2 citation statements)

References 68 publications

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“…9 In this context, a myriad of possibilities has been explored for the photocatalytic generation of carbamoyl radicals (Scheme 1B). For example, the photoinduced oxidation of oxamic acids [10][11][12][13][14] with concomitant decarboxylation or semicarbazides with loss of N2 15 has been reported in recent years. On the other hand, photooxidation of 4-carboxamido-1,4-dihydropyridines has proved to be a competent method to obtain carbamoyl radicals but generate the corresponding pyridine as waste.…”

Section: Introductionmentioning

confidence: 99%

Carbamoylation of azaarenes and olefins with formamides through dual photoredox/HAT catalysis

Martos,

Quevedo-Flores,

Laze

et al. 2024

Preprint

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Among the different methods to synthesize amides, radical amidation of suitable acceptors is appealing. In this context, we have developed a methodology for the photoinduced Minisci and Giese carbamoylation with readily available formamides. This approach avoids using less atom-efficient carbamoyl precursors (e.g., oxamic acids) and sacrificial oxidants, relying on dual photoredox/hydrogen atom transfer (HAT) catalysis.

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Section: Introductionmentioning

confidence: 99%

Carbamoylation of azaarenes and olefins with formamides through dual photoredox/HAT catalysis

Martos,

Quevedo-Flores,

Laze

et al. 2024

Preprint

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“…The previous reports on Truce–Smiles-type rearrangement of N -aryl amides via C(aryl)–N bond cleavage infer that the intramolecular ipso attack of intermediate A , generated from carbamoyl radicals and alkenes, should proceed efficiently. However, it is a challenging process as the intermediate A preferentially transforms into compound 4 or compound 5 by the intramolecular radical addition at the ortho -position of the aromatic carbon . Therefore, to achieve selective ipso attack a bulky substituent on the nitrogen atom of the N -amide group is introduced .…”

mentioning

confidence: 99%

Carbamoylarylation of Alkenes with N-Aryl Oxamic Acids Involving 1,4-Aryl Migration Via C(aryl)–N Bond Cleavage

Shiozuka,

Wu,

Kawashima

et al. 2024

ACS Catal.

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We report carbamoylarylation of alkenes using Naryl oxamic acid derivatives under visible-light irradiation. Reactions of alkenes with carbamoyl radicals generated using Naryl oxamic acid derivatives to afford Giese-type products or 3,4dihydroquinolin-2(1H)-ones via ortho-radical addition to an aryl amide moiety have been previously reported. However, this study reveals that the introduction of a removable bulky group onto the nitrogen atom of N-aryl oxamic acids facilitates the radical addition of carbamoyl radicals to alkenes, resulting in 1,4-aryl migration via C(aryl)−N bond cleavage, thus affording arylpropanamides. Various alkenes, such as acrylic acid and styrene derivatives, are successfully applied to the synthesis of a variety of arylpropanamide derivatives, including 1,4-dicarbonyl amides, forming two C−C bonds.

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Site‐Selective Construction of N‐Linked Glycopeptides through Photoredox Catalysis

Wei,

Huang,

Wang

et al. 2024

Angewandte Chemie

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The glycosylation of peptides and proteins can significantly impact their intrinsic properties, such as conformation, stability, antigenicity, and immunogenicity. Current methods for preparing N‐linked glycopeptides typically rely on amide bond formation, which can be limited by the presence of reactive functional groups like acids and amines. Late‐stage functionalization of peptides offers a promising approach to obtaining N‐linked glycopeptides. In this study, we demonstrate the preparation of N‐linked glycopeptides through a photoredox‐catalyzed site‐selective Giese addition between N‐glycosyl oxamic acid and peptides containing dehydroalanine (Dha) under visible light conditions. Unlike traditional methods that rely on the coupling of aspartic acid and glycosylamine, this approach utilizes the conjugation of N‐glycosylated carbamoyl radicals with Dha, facilitating the straightforward modification of complex peptides.

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Direct decarboxylative Giese amidations: photocatalytic vs. metal- and light-free

Abstract: A direct intermolecular decarboxylative Giese amidation reaction from bench stable, non-toxic and environmentally benign oxamic acids has been developed, which allows for easy access to 1,4-difunctionalised compounds which are not...

Cited by 14 publications

References 68 publications

Carbamoylation of azaarenes and olefins with formamides through dual photoredox/HAT catalysis

Carbamoylation of azaarenes and olefins with formamides through dual photoredox/HAT catalysis

Carbamoylarylation of Alkenes with N-Aryl Oxamic Acids Involving 1,4-Aryl Migration Via C(aryl)–N Bond Cleavage

Site‐Selective Construction of N‐Linked Glycopeptides through Photoredox Catalysis

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