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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Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(9), С. 3565 - 3574

Опубликована: Фев. 16, 2024

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign method fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination carboxylic acids to mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This facilitated high product yields in short reaction times even sterically challenged acids. We also realized coupling and amines as well TFEDMA-mediated direct with via sequential one-pot deoxyfluorination/coupling pathway. Furthermore, protocol was expanded include peptide synthesis. The efficiency protocol, terms speed, characteristics, favorable E-factor, aligns requirements current environmental policies.

Язык: Английский

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Rapid peptide synthesis using a methylimidazolium sulfinyl fluoride salt

Communications Chemistry, Год журнала: 2025, Номер 8(1)

Опубликована: Фев. 22, 2025

Peptide couplings have been a subject of investigation for over century, with modern research seeking to discover new methodologies that minimize purification steps, reagent expense, and/or decrease reaction times. Of the numerous coupling reagents available, sulfur(IV) fluorides potential as they can effectively transform carboxylic acids reactive intermediates, and sulfite by-products be removed through aqueous washes. Here we demonstrate formation capture key acyl fluorosulfite intermediates peptide in 15 min total, without epimerization or column chromatography purification. Dipeptides were obtained 40–94% yields. This approach was expanded longer chains iterative couplings, oligopeptides 24–57% yields, each within 2 days. Mechanistic studies indicate does not proceed fluoride instead involves nucleophilic catalysis. The mild conditions are tolerant wide range protecting groups canonical non-canonical amino acids. Peptides known important therapeutics; however, minimizing times methods remains challenging. Here, authors use reagent, demonstrating rapid purification, achieving yields dipeptides oligopeptide formation.

Язык: Английский

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Activation of Carboxylic Acids by using Sulfonyl Chloride Reagent: A Simple One Pot Conversion of Carboxylic Acids to Alcohols

Organic Preparations and Procedures International, Год журнала: 2025, Номер unknown, С. 1 - 12

Опубликована: Апрель 18, 2025

Язык: Английский

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In-Flow Generation of Thionyl Fluoride (SOF₂) Enables the Rapid and Efficient Synthesis of Acyl Fluorides from Carboxylic Acids

JACS Au, Год журнала: 2024, Номер 4(8), С. 2989 - 2994

Опубликована: Июль 12, 2024

Herein, we report an approach for generating thionyl fluoride (SOF

Язык: Английский

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One-pot ester and thioester formation mediated by pentafluoropyridine (PFP)

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(41), С. 8059 - 8064

Опубликована: Янв. 1, 2022

The use of pentafluoropyridine (PFP) is reported in ester and thioester coupling reactions. reaction proceeds via an situ generated acyl fluoride intermediate.

Язык: Английский

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Thionyl Fluoride as a Sulfur(IV) SuFEx Hub for the Efficient Syntheses of Sulfinamides and Sulfinate Esters

Chemical Communications, Год журнала: 2024, Номер 60(72), С. 9765 - 9768

Опубликована: Янв. 1, 2024

Herein, we demonstrate a method for the syntheses of sulfinamides and sulfinate esters using novel sulfur(IV) fluoride exchange reaction with organometallic reagents. Our strategy involves addition an amine or alcohol nucleophile to thionyl fluoride, acting as S(IV) SuFEx hub, followed by reagent. This approach allows efficient access (45-91% yields) (44-82% in only 30 minutes. The sulfinamide also can be readily derivatized corresponding S(VI) sulfonamides, sulfonate esters, sulfonimidamides, sulfonimidates without isolation intermediates.

Язык: Английский

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Sulfur(iv) reagents for the SuFEx-based synthesis of substituted sulfamate esters

Chemical Science, Год журнала: 2023, Номер 14(7), С. 1775 - 1780

Опубликована: Янв. 1, 2023

Sulfur(vi) fluoride exchange chemistry has been reported to be effective at synthesizing valuable sulfur(vi) functionalities through sequential nucleophilic additions, yet oxygen-based nucleophiles are limited in this approach phenolic derivatives. Herein, we report a new sulfur(iv) strategy access synthetically challenging substituted sulfamate esters from alkyl alcohols and amines. We also the development of non-gaseous, reagent, N-methylimidazolium sulfinyl hexafluorophosphate (MISF). By leveraging reactivity center novel addition amines MISF followed by oxidation afforded desired sulfamates 40-83% yields after two steps. This expands scope SuFEx increasing accessibility underdeveloped -S(O)F intermediates for future explorations.

Язык: Английский

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Efficient Amide Formation from Non‐Activated Cyclopropyl Ester via Acyl Fluoride Generation Using Hypervalent Iodine(III) Reagent and Selectfluor

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(9)

Опубликована: Июль 27, 2023

Abstract A novel and unique activation method for esters possessing a non‐activated cyclopropyl moiety as potential activating group is developed acyl fluoride generation using hypervalent iodine(III) reagent Selectfluor. The resulting fluoride, which versatile synthetic intermediate, was smoothly transformed into the various carbonyl compounds, in particular, amides. This protocol can be applied to chemoselective of diester compounds.

Язык: Английский

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AITF (4-acetamidophenyl triflimide) mediated synthesis of amides, peptides and esters

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(44), С. 8875 - 8882

Опубликована: Янв. 1, 2023

AITF is a stable, crystalline solid that used for the construction of amide, peptide and ester bonds. The utility synthesis summarized.

Язык: Английский

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