Mechanochemical Synthesis of Amides with Uronium-Based Coupling Reagents: A Method for Hexa-amidation of Biotin[6]uril

Dalidovich, Tatsiana; Mishra, Kamini A.; Shalima, Tatsiana; Kudrjašova, Marina; Kananovich, Dzmitry G.; Aav, Riina

doi:10.1021/acssuschemeng.0c05558

Cited by 40 publications

(56 citation statements)

References 90 publications

(208 reference statements)

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“…Ball milling experiments were performed in a Form‐Tech Scientific FTS1000 shaker mill operating at 30 Hz using a 14 mL zirconia‐coated milling jar and a single 10 mm milling ball. In contrast to amide synthesis, [41] attempted in‐situ activation of alcohol 1 with TCFH and TFFH reagents in the presence of morpholine resulted in a very low yield of 2 (less than 8 %; see Table S1 in the Supporting Information). This result is an outcome of a faster competitive reaction of halouronium reagents with morpholine itself [52,53] .…”

Section: Resultsmentioning

confidence: 99%

“…Thus, a stimulant drug 1‐methyl‐4‐benzylpiperazine ( 36 , MBZP) was prepared by alkylation of N ‐methylpiperazine ( 37 ) with benzylic alcohol and isolated in 54 % yield by crystallization of its hydrochloric salt from methanol (Scheme 5). Antidepressant piberaline ( 38 ) was prepared from picolinic acid ( 39 ) via stepwise mechanochemical amide coupling, [41] solvent‐free Boc‐deprotection, [60] and mechanochemical amination steps. Derivatives of 4‐(hydroxymethyl)benzoic acid ( 42 ) have multiple pharmaceutical uses, including anticancer agents (e. g., Imanitib, [61] Masitinib [62] ), histone deacetylase inhibitors, [63] histamine receptor antagonists (e. g., Bavisant) [64] .…”

Section: Resultsmentioning

confidence: 99%

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Mechanochemical Nucleophilic Substitution of Alcohols via Isouronium Intermediates**

et al. 2022

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An expansion of the solvent‐free synthetic toolbox is essential for advances in the sustainable chemical industry. Mechanochemical reactions offer a superior safety profile and reduced amount of waste compared to conventional solvent‐based synthesis. Herein a new mechanochemical method was developed for nucleophilic substitution of alcohols using fluoro‐N,N,N′,N′‐tetramethylformamidinium hexafluorophosphate (TFFH) and K2HPO4 as an alcohol‐activating reagent and a base, respectively. Alcohol activation and reaction with a nucleophile were performed in one milling jar via reactive isouronium intermediates. Nucleophilic substitution with amines afforded alkylated amines in 31–91 % yields. The complete stereoinversion occurred for the SN2 reaction of (R)‐ and (S)‐ethyl lactates. Substitution with halide anions (F−, Br−, I−) and oxygen‐centered (CH3OH, PhO−) nucleophiles was also tested. Application of the method to the synthesis of active pharmaceutical ingredients has been demonstrated.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Mechanochemical Nucleophilic Substitution of Alcohols via Isouronium Intermediates**

et al. 2022

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“…resulted in an increase from 8 % to full conversion. On the other hand, alternative bases N ‐methylmorpholine (NMM), diisopropylethylamine (DIEA), and N ‐methylimidazole (NMI) [60,61] all gave low conversions (entries 16–18). Finally, in an attempt to minimize the amount of AA, the coupling was carried out at 1.3 and 1.2 equiv.…”

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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“…This type of reactor technology is very effective at homogenizing reactions mixtures (mixing) and inputting energy in the form of heat and pressure to reaction centres. All of this can be largely achieved in the absence of solvent, and thus the reactor environment of a ball mill is receiving increasing interest in recent times [32–60] …”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Organocatalysis: Do High Enantioselectivities Contradict What We Might Expect?

Williams¹,

Morrill²,

Browne

2021

ChemSusChem

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Ball mills input energy to samples by pulverising the contents of the jar. Each impact on the sample or wall of the jar results in an instantaneous transmission of energy in the form of a temperature and pressure increase (volume reduction). Conversely, enantioselective organocatalytic reactions proceed through perceived delicate and well‐organised transition states. Does there exist a dichotomy in the idea of enantioselective mechanochemical organocatalysis? This Review provides a survey of the literature reporting the combination of organocatalytic reactions with mechanochemical ball milling conditions. Where possible, direct comparisons of stirred in solution, stirred neat and ball milled processes are drawn with a particular focus on control of stereoselectivity.

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Mechanochemical Synthesis of Amides with Uronium-Based Coupling Reagents: A Method for Hexa-amidation of Biotin[6]uril

Abstract: Solid-state reactions using mechanochemical activation have emerged as solvent-free atom-efficient strategies for sustainable chemistry. Herein we report a new mechanochemical approach for the amide

Cited by 40 publications

References 90 publications

Mechanochemical Nucleophilic Substitution of Alcohols via Isouronium Intermediates**

Mechanochemical Nucleophilic Substitution of Alcohols via Isouronium Intermediates**

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

Mechanochemical Organocatalysis: Do High Enantioselectivities Contradict What We Might Expect?

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