Direct formation of amide/peptide bonds from carboxylic acids: no traditional coupling reagents, 1-pot, and green

Chemical Science, Год журнала: 2023, Номер 14(13), С. 3462 - 3469

Опубликована: Янв. 1, 2023

Technology for generating especially important amide and peptide bonds from carboxylic acids amines that avoids traditional coupling reagents is described. The 1-pot processes developed rely on thioester formation, neat, using a simple dithiocarbamate, are safe green, Nature-inspired thioesters then converted to the targeted functionality.

Язык: Английский

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On the Use of Triarylsilanols as Catalysts for Direct Amidation of Carboxylic Acids

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(14), С. 9853 - 9869

Опубликована: Июль 11, 2023

Triarylsilanols have been reported as the first silicon-centered molecular catalysts for direct amidation of carboxylic acids with amines identified after a screen silanols, silanediols, disiloxanediols, and incompletely condensed silsesquioxanes potential homogeneous catalysts. Subsequent synthesis testing various electronically differentiated triarylsilanols tris(p-haloaryl)silanols more active than parent triarylsilanol, where bromide congener is found to be most active. Catalyst decomposition can observed by NMR methods, but RPKA methods reveal that product inhibition operative, tertiary amides are inhibitory secondary amides. Studies using an authentically synthesized triaryl silylester putative intermediate in catalytic system enable plausible mechanism proposed supported computationals.

Язык: Английский

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Silyl Esters as Reactive Intermediates in Organic Synthesis

Synthesis, Год журнала: 2023, Номер 55(20), С. 3209 - 3238

Опубликована: Апрель 28, 2023

Abstract Silyl esters have been exploited as metastable reaction intermediates, both purposefully and unintentionally, since at least the 1960s. Their reactivity is broadly related to substituents on silicon, in this way their properties can be readily modulated. unique profiles that used generate downstream products of a range functionalities, because many excellent methods for synthesis variety value-added chemicals developed. Furthermore, frequent use hydrosilanes terminal reductants catalytic processes, silyl ester intermediates are likely more commonly utilized by synthetic chemists than currently realized. This review comprehensively summarizes reactions known take advantage reactive discusses examples proceed an unanticipated manner through intermediates. 1 Introduction 2 Synthesis Esters 3 Making Amides from 3.1 Amidation Using Chlorosilanes 3.2 Azasilanes 3.3 Oxysilanes 3.4 Hydrosilanes 3.5 Amine Formation via Amidation/Reduction 3.6 Miscellaneous 4 Mechanistic Investigations 4.1 Mechanism 4.2 4.3 Oxy- or 5 6 Aldehydes, Alcohols, Amines, Alkanes Reduction 6.1 Aldehyde Metal-Free 6.2 Metal-Mediated 6.3 Alcohol 6.4 6.5 Alkane 7 Acid Chlorides 8 In Situ Generated Ramifications Catalysis 9 Conclusion

Язык: Английский

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Organoboron catalysis for direct amide/peptide bond formation

Chemical Communications, Год журнала: 2024, Номер 60(80), С. 11202 - 11222

Опубликована: Янв. 1, 2024

This review explores studies on the development of direct dehydrative amide/peptide bond formation from carboxylic acids using organoboron catalysis.

Язык: Английский

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Amides and Lactams

Elsevier eBooks, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

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Catalytic and Sustainable Amide Bond Formation using a DABCO/Dichlorotriazine System

ChemCatChem, Год журнала: 2023, Номер 15(10)

Опубликована: Апрель 14, 2023

Abstract Amides are one of the most important functional groups in organic chemistry and play essential roles both pharmaceutical industry life sciences. However, due to natural reactivity carboxylic acids amines, their direct coupling is challenging often leads reactions that not atom‐economic produce large amounts non‐recoverable by‐products. Despite impressive number reagents available, sustainable methods for amide bond formation still needed. To address this challenge, a new catalytic approach preparation amides from amines reported here. This method combines organocatalysis with substoichiometric amount activating agent under mild conditions (open air, room temperature, green solvents). was applied good efficiency on wide range substrates, without epimerization chiral stereocenters SPPS.

Язык: Английский

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Concise Synthesis of 2,5-Diketopiperazines via Catalytic Hydroxy-Directed Peptide Bond Formations

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(11), С. 6901 - 6910

Опубликована: Май 1, 2023

2,5-Diketopiperazines (DKPs) with hydroxymethyl functional groups are essential structures found in many bioactive molecules and materials. We have established a simple protocol for the concise synthesis of this type DKPs through diboronic acid anhydride-catalyzed hydroxy-directed peptide bond formations. The sequential reactions report, which consist three steps, an intermolecular catalytic condensation reaction water is only byproduct, deprotection nitrogen-protecting group, intramolecular cyclization, enabled functionalized high to excellent yields without any intermediate purification. utility has been demonstrated by synthesizing natural products, phomamide Cyclo(Deala-l-Leu).

Язык: Английский

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Rapid Synthesis of Peptides Mediated by PPh₃−I₂

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер 13(8)

Опубликована: Апрель 24, 2024

Abstract We report a mild, operationally simple, convenient, and rapid method of peptide bond formation using triphenylphosphine iodine. The developed protocol was utilized to couple coded, non‐coded, challenging amino acids in 64–92 % yield. Sterically hindered α,α‐disubstituted acids, which are important constituents natural peptides, were also coupled good Mild reaction conditions open air produce bonds short time (30 min) without racemization.

Язык: Английский

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Improved Electrochemical Peptide Synthesis Enabled by Electron‐Rich Triaryl Phosphines

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 10, 2024

Abstract While remarkable progress has been made in the development of peptide medicines, many problems related to synthesis remain unresolved. Previously, we reported electrochemical using a phosphine as potentially recyclable coupling reagent. However, there was room for improvement from point view reaction efficiency, especially carboxylic acid activation step and bond formation step. To overcome these challenges, searched optimal phosphine. Among phosphines with various electronic properties, found that electron‐rich triaryl improved efficiency. Consequently, successfully performed on sterically hindered valuable amino acids. We also synthesized oligopeptides were challenging our previous method. Finally, examined effect substituents cations, gained some insights into reactivity, which will aid researchers designing reactions involving cations.

Язык: Английский

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DMAPO/Boc₂O‐Mediated One‐Pot Direct N1‐Acylation of Indazole with Carboxylic Acids: A Practical Synthesis of N1‐Functionalized Alkyl Indazoles

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(18)

Опубликована: Фев. 15, 2024

Abstract This report describes the one‐pot direct N ‐acylation of indazole with carboxylic acids using our previously developed 4‐( , ‐dimethylamino)pyridine ‐oxide (DMAPO)/di‐ tert ‐butyl dicarbonate (Boc 2 O) system. simple system provides 1‐acyl indazoles in high yield 1 selectivities and does not require use activated derivatives or temperatures. new method exhibits a wide substrate scope (>40 examples). In addition, synthesis 1‐functionalized alkyl utilizing as starting materials was achieved. stepwise protocol is useful for selective structurally diverse indazoles, which are difficult to synthesize by other methods such Mitsunobu reaction classical S alkylation indazole.

Язык: Английский

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