Simple Synthesis of Amides via Their Acid Chlorides in Aqueous TPGS-750-M

Shi, Min; Ye, Ning; Chen, Wei; Wang, Hui; Cheung, C. K.; Parmentier, Michaël; Gallou, Fabrice; Wu, Bin

doi:10.1021/acs.oprd.0c00303

Cited by 33 publications

(19 citation statements)

References 35 publications

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“…Recently, we have also demonstrated the amidation reaction of water sensitive acyl chloride with amines under micellar condition. 51 In aforementioned methodology, most of the products are crystallized out from the reaction mixture and purified thorough simple filtration and washing with water. However, these methods require prefunctionalized acid chlorides or explosive activators, such as HOAt or HOBt, a severe limitation for their application on scale.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Water: An Underestimated Solvent for Amide Bond-Forming Reactions

Hazra

Gallou

Handa

2022

ACS Sustainable Chem. Eng.

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Construction of the amide/peptide bond is one of the most encountered transformations in the pharmaceutical and chemical industries. Traditional protocols rely on the use of undesirable organic solvents, such as N,N-dimethylformamide (DMF), N-methyl pyrrolidone (NMP), or dichloromethane (CH 2 Cl 2 ). These solvents adversely impact the environment, workers' safety, and health. This has led academia and industry to search and develop greener and more sustainable amide forming synthetic protocols to increase performance in terms of yield and selectivity and avoid or reduce the dependency in these hazardous solvents. The following account discusses the recent development of amide/peptide bond formation in water.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Water: An Underestimated Solvent for Amide Bond-Forming Reactions

Hazra

Gallou

Handa

2022

ACS Sustainable Chem. Eng.

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“…We first assessed the efficient CA for cumbersome couplings, HDMC (6‐chloro‐1‐((dimethylamino)(morpholino)‐methylene)‐1H‐benzotriazolium hexafluorophosphate 3‐oxide), [57] which gave a low conversion (entry 8). As acid chlorides were recently used in aqueous amide bond formations [31g] we examined the acid chloride‐forming DMCH (N‐(chloro(morpholino)methylene)‐N‐methylmethanaminium hexafluorophosphate), [57] and gratifyingly, a marked increase in conversion was observed (entry 9). In fact, TCFH (N,N,N′,N′‐Tetramethylchloroformamidinium hexafluorophosphate) [58] gave a substantial improvement (entry 10) over COMU (entry 2) as well, while TFFH [59] gave a low conversion (entry 11).…”

Section: Methodsmentioning

confidence: 99%

Circular Aqueous Fmoc/t‐Bu Solid‐Phase Peptide Synthesis

Pawlas

Rasmussen

2021

ChemSusChem

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Circular economy and aqueous synthesis are attractive concepts for sustainable chemistry. Here it is reported that the two can be combined in the universal method for peptide chemistry, fluorenylmethoxycarbonyl(Fmoc)/t‐Bu solid‐phase peptide synthesis (SPPS). It was demonstrated that Fmoc/t‐Bu SPPS could be performed under aqueous conditions using standard Fmoc amino acids (AAs) employing TentaGel S as resin and 4 : 1 mixture of water with inexpensive green solvent PolarClean. This resin/solvent combination played a crucial dual role by virtue of improving resin swelling and solubility of starting materials. In a model coupling, TCFH and 2,4,6‐collidine afforded a full conversion at only 1.3 equiv. AA, and these conditions were used in SPPS of Leu enkephaline amide affording the model peptide in 85 % yield and 86 % purity. A method to recycle the waste by filtration through a mixed ion exchange resin was developed, allowing reusing the waste without affecting quality of the peptide. The method herein obviates the use of unconventional or processed AAs in aqueous SPPS while using lower amounts of starting materials. By recycling/reusing SPPS waste the hazardous dipolar aprotic solvents used in SPPS were not only replaced with an aqueous medium, solvent use was also significantly reduced. This opens up a new direction in aqueous peptide chemistry in which efficient use of inexpensive starting materials and waste minimization is coupled with the universal Fmoc/t‐Bu SPPS.

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“…92,93 In 2020, Wu et al used TPGS-750-M to synthesize the amide bond from acyl chlorides and amines under aqueous micellar conditions. 94 All the reactions proceeded in 2 wt% TPGS-750-M aqueous solution in the presence of DIPEA as the base, affording the corresponding amides in moderate to good conversion rates in less than 2 h. At the end of the reaction, the product was easily obtained in high purity by either direct filtration or extraction from the reaction mixture. The remaining 2 wt% TPGS-750-M aqueous solution was recycled, allowing to reduce the PMI value of the process.…”

Section: Reviewmentioning

confidence: 99%