Direct Amidation of Carboxylic Acids with Tertiary Amines: Amide Formation over Copper Catalysts through C–N Bond Cleavage

Xiong, Biquan; Zhu, Longzhi; Feng, Xiaofeng; Lei, Jian; Chen, Tieqiao; Zhou, Yongbo; Han, Lu; Au, Chak Tong; Yin, Shuang

doi:10.1002/ejoc.201402332

Cited by 28 publications

(12 citation statements)

References 32 publications

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“…Further deprotonation and rearrangement form 121 and regenerate HOAc. The reductive elimination of 121 affords the final product 117 and regenerates the Cu catalyst to complete the catalytic cycle.A similar aerobic oxidative amidation of tertiary amines with 2-phenylacetonitrile derivatives was described by Yin et al (Scheme 39a) 141,142. This one-pot reaction involves C−C bond activation, C−N bond cleavage, and C−H bond oxygenation.…”

mentioning

confidence: 84%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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mentioning

confidence: 84%

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

et al. 2015

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“…Simple catalytic systems, employing first row transition metals without ligands, for example, salts such as NiCl 2, [93] FeCl 3 , [90] and CuI 89 have been shown to be capable amidation catalysts, however, they suffer from requiring elevated temperatures or undesirable solvents such as CCl 4. [89] A heterogeneous catalyst, TiO 2 , is cheap and widely available and capable of microwave assisted, solvent free amidation of neat carboxylic acids. [95] This method also showed facile catalyst recovery from the reaction mixture.…”

Section: Other Metalsmentioning

confidence: 99%

“…Unfunctionalized silica has also been reported to catalyze amidation when it is in a pristine (thermally untreated) state. [101] The [87] Al/Zr/Ti-SBA-15 Toluene 110 50* None Fontaine [88] CuI DMF 60 5 None Yin [89] FeCl 3 Toluene 75 20 None Sureshbabu [90] HfCp 2 Cl 2 Et 2 O r.t. 10 4 Å M.S. Adolfsson [80] N 2 O 5 Toluene 40 50* None Shimizu [91] (NH 4 ) 2 Ce(NO 3 ) 6 Neat Microwave 2 None Markiewicz [92] NiCl 2 Toluene 110 10 None Huang [93] Ta(OMe) 5 Neat 40 10 None Yamamoto [94] TiCp 2 Cl 2 THF 70-80 10 4 Å M.S.…”

Section: Other Metalsmentioning

confidence: 99%

Recent developments in catalytic amide bond formation

Todorovic

Perrin

2020

Peptide Science

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Amide bond forming reactions are critical for both polypeptide synthesis and medicinal chemistry. Most current approaches for amidation employ stoichiometric activating agents, but such methods are neither atom economical nor synthetically elegant. Catalytic approaches for amidation are potentially green and more ideal substitutes for current standard methods and thus are the subject of this review. Such methods face significant thermodynamic and kinetic barriers and have, as a result, historically

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“…The Yin group used tertiary amines as precursors of nucleophilic amino‐copper intermediates 56.4 for amidation 56.1 (Eq. 56‐1).…”

Section: Electrophilic Acidsmentioning

confidence: 99%

Arylacetic Acids in Organic Synthesis

et al. 2019

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Arylacetic acids are widely used in organic reactions and their recent advances are summarized in six categories according to their triggered pathways: (1) the acid as directing group in ortho-or meta-CÀ H activation; (2) decarboxylation; (3) deprotonation; (4) nucleophilic methylenes; (5) nucleophilic acids; (6) electrophilic acids. Reactions with alkenes, alkynes, aldehydes, amines, water, Grignard reagents, silanes and so forth are discussed. We hope this Minireview will promote future research in this area. Recently, the Zeng group [3g] reported a weakly coordinationassisted alkynylation of arylacetic acids with iridium catalysis under air atmosphere (Eq. 2-2). It was supported the sixmembered ring cycloiridiated 2.5 acted as the key intermediate. The alkynylation of indole, thiophene, pyrrole, and benzo[b] thiophene afforded better yields than phenylacetic acids. The acid moiety could also participated in the intramolecular ortho-CÀ H activation, which was developed by the Shi group to obtain lactonization 2.6 (Eq. 2-3) (Scheme 2). Meta-CÀ H ArylationThe study of Yu group [3e] in 2017 revealed a successful control of meta selectivity 3.1 of arylation from aryl iodides (Eq. 3-1). The use of mono-protected 3-amino-2-hydroxypyridine (as ligand) and 2-carbomethoxynorbornene (NBE-CO 2 Me) were crucial. In the absence of NBE-CO 2 Me, only ortho-arylated product was obtained. This method was still efficient in a gramsale (Scheme 3). Decarboxylation Decarboxylative CouplingAs shown in Scheme 4, the decarboxylation could generate benzyl radicals 4.1. Then, direct couplings of 4.1 with diverse [ + ] These authors contributed equally. Scheme 1. Six categories based on triggered mechanism. 2 3 4 5 6 7 8 . Passerini Three-Component ReactionThe Passerini reaction was the oldest multicomponent reaction (MCR) [37d] in which isocyanides, carboxylic acids and aldehydes were used. It was powerful for the rapid construction of complex molecules. The tactic to expand the scope of Passerini reaction was to use surrogates of the carbonyl partners. As described in Scheme 51, syn-chlorooximes, [37b] diazoketones, [37c] alcohols, [37d,e] azirines [37f] and isatins [37g] could be employed instead of aryl or alkyl aldehydes [37a] (Scheme 51). Besides, in 2018, Zhang and co-workers [37] have firstly reported asymmetric phosphoric acid-catalyzed four-component Ugi reaction, which Scheme 45. BTM-catalyzed cycloaddition. Scheme 46. HBTM-catalyzed cycloaddition. Scheme 47. TFA-catalyzed reaction. Scheme 48. Friedel-Crafts triggered tandem reactions. Scheme 49. C-acylation of 1,3-diones. Scheme 50. C-acylation of 1,3-indandiones.

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Direct Amidation of Carboxylic Acids with Tertiary Amines: Amide Formation over Copper Catalysts through C–N Bond Cleavage

Cited by 28 publications

References 32 publications

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Transition-Metal-Catalyzed Cleavage of C–N Single Bonds

Recent developments in catalytic amide bond formation

Arylacetic Acids in Organic Synthesis

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