Mechanism of arylboronic acid-catalyzed amidation reaction between carboxylic acids and amines

Unprotected keto- and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly-substituted N-alpha-secondary (2°) and tertiary (3°) hydroxylamines. The method’s synthetic utility is demonstrated with the total synthesis of the trace alkaloid N-methyl-euphococcine. Preliminary experimental and computational mechanistic studies point toward the formation of a boroxine as the active allylating species.

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Amidation Reaction of Quinoline‐3‐carboxylic Acids with Tetraalkylthiuram Disulfides under Simple Conditions: A facile Synthesis of Quinoline‐3‐carboxamides

Asian Journal of Organic Chemistry ◽

10.1002/ajoc.202000462 ◽

2020 ◽

Vol 9 (12) ◽

pp. 2191-2195

Author(s):

Jingyan Hu ◽

Xiefeng Ye ◽

Shuai Hao ◽

Qianrui Zhao ◽

Mingqin Zhao ◽

...

Keyword(s):

Carboxylic Acids ◽

Facile Synthesis ◽

Amidation Reaction

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Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

Nature Communications ◽

10.1038/s41467-021-24908-w ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Yunyun Ning ◽

Shuaishuai Wang ◽

Muzi Li ◽

Jie Han ◽

Chengjian Zhu ◽

...

Keyword(s):

Carboxylic Acids ◽

Functional Group ◽

Amide Bond ◽

Coupling Reagents ◽

Complex Molecules ◽

Bond Forming ◽

Synergistic Catalysis ◽

Wide Range ◽

Amidation Reaction ◽

Forming Methods

AbstractDevelopment of catalytic amide bond-forming methods is important because they could potentially address the existing limitations of classical methods using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction of carboxylic acids with nitroarenes and nitroalkanes enabled by the triplet synergistic catalysis of FeI2, P(V)/P(III) and photoredox catalysis, which avoids the production of byproducts from stoichiometric coupling reagents. A wide range of carboxylic acids, including aliphatic, aromatic and alkenyl acids participate smoothly in such reactions, generating structurally diverse amides in good yields (86 examples, up to 97% yield). This Umpolung amidation strategy opens a method to address challenging regioselectivity issues between nucleophilic functional groups, and complements the functional group compatibility of the classical amidation protocols. The synthetic robustness of the reaction is demonstrated by late-stage modification of complex molecules and gram-scale applications.

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A solvent-dependent chirality-switchable thia-Michael addition to α,β-unsaturated carboxylic acids using a chiral multifunctional thiourea catalyst

Chemical Science ◽

10.1039/d0sc01729a ◽

2020 ◽

Vol 11 (21) ◽

pp. 5572-5576 ◽

Cited By ~ 1

Author(s):

Noboru Hayama ◽

Yusuke Kobayashi ◽

Eriko Sekimoto ◽

Anna Miyazaki ◽

Kiyofumi Inamoto ◽

...

Keyword(s):

Carboxylic Acids ◽

Tertiary Amine ◽

Michael Addition ◽

Arylboronic Acid ◽

Unsaturated Carboxylic Acids

An asymmetric thia-Michael addition of arylthiols to α,β-unsaturated carboxylic acids using a thiourea catalyst that bears arylboronic acid and tertiary amine moieties is reported.

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Preparation of mono- and diacetyl 4,4′-dimethylbiphenyl and their corresponding carboxylic acids: Reactivity, selectivity and isomer distribution studies via Lewis acid catalyzed Friedel-Crafts acetylation/oxidation

Journal of Molecular Catalysis A Chemical ◽

10.1016/j.molcata.2007.03.069 ◽

2007 ◽

Vol 273 (1-2) ◽

pp. 169-176 ◽

Cited By ~ 3

Author(s):

Salam J.J. Titinchi ◽

Fadhil S. Kamounah ◽

Hanna S. Abbo

Keyword(s):

Carboxylic Acids ◽

Lewis Acid ◽

Isomer Distribution ◽

Acid Catalyzed ◽

Distribution Studies

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Isocarbostyrils. II. The Conversion of 2-Methyl-4-acyl-5-nitroisocarbostyrils to 2-Substituted Indole-4-carboxylic Acids

Canadian Journal of Chemistry ◽

10.1139/v71-465 ◽

1971 ◽

Vol 49 (17) ◽

pp. 2797-2802 ◽

Cited By ~ 6

Author(s):

D. E. Horning ◽

G. Lacasse ◽

J. M. Muchowski

Keyword(s):

Sulfuric Acid ◽

Carboxylic Acid ◽

Carboxylic Acids ◽

Alkaline Hydrolysis ◽

Mannich Reaction ◽

Reductive Cyclization ◽

Acid Catalyzed ◽

Acid Anhydrides ◽

Hydrolysis Of ◽

Derivatives Of

The sulfuric acid catalyzed acylation of 2-methyl-5-nitroisocarbostyril with carboxylic acid anhydrides gave the corresponding 4-acylated derivatives 3, which underwent reductive cyclization to 2-substituted derivatives of 4-methyl-1,3,4,5-tetrahydropyrrolo[4.3.2.de]isoquinolin-5-one (4). Alkaline hydrolysis of the six-membered lactam in 4 was accompanied by a retro-Mannich reaction to produce 2-substituted indole-4-carboxylic acids in about 40 % overall yield from 3.

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