Methyltrimethoxysilane (MTM) as a Reagent for Direct Amidation of Carboxylic Acids

Braddock, D. Christopher; Davies, Joshua J.; Lickiss, Paul D.

doi:10.1021/acs.orglett.1c04265

Cited by 19 publications

(15 citation statements)

References 58 publications

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“… 3 Accordingly, novel amidation protocols have been reported in recent years which avoid the use of toxic, sensitizing, and atom inefficient coupling reagents. 4 These methods include the amidation of carboxylic acids via the corresponding acyl fluorides 5 or by the direct condensation of unactivated carboxylic acids with amines using silicon reagents 6 or utilizing boron, 7 transition metal, 8 or photoredox catalysis. 9 Alternative strategies involve the direct amidation of esters, 10 the oxidative amidation of aldehydes, 11 or palladium-catalyzed carbonylation of aryl halides.…”

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confidence: 99%

Functionalized Tetrazoles as Latent Active Esters in the Synthesis of Amide Bonds

et al. 2022

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We report the use of N-2,4-dinitrophenyltetrazoles as latent active esters (LAEs) in the synthesis of amide bonds. Activating the tetrazole generates an HOBt-type active ester without the requirement for exogenous coupling agents. The methodology was widely applicable to a range of substrates, with up to quantitative yields obtained. The versatility and functional group tolerance were exemplified with the one-step synthesis of various pharmaceutical agents and the N-acylation of resin-bound peptides.

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confidence: 99%

Functionalized Tetrazoles as Latent Active Esters in the Synthesis of Amide Bonds

et al. 2022

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“…In 2022, the Kumar group reported an inorganic base (KPF 6 ) as an efficient catalyst for this transformation (Scheme 12). [43] Under the optimized conditions, a wide range of amides (68) were produced in good to excellent yields, ranging from 55 % to 88 %. Further investigations revealed that an acid derivative (66 or 67) was detected as an intermediate during the reaction process and potassium ion had no significant effect on this reaction.…”

Section: The Catalytic Amidation Of Carboxylic Acids With Aminesmentioning

confidence: 99%

Recent Advances in Carbon‐Nitrogen/Carbon‐Oxygen Bond Formation Under Transition‐Metal‐Free Conditions

Zhang

Song

Shi

et al. 2023

The Chemical Record

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Carbon‐heteroatom bond formation under transition‐metal free conditions provides a powerful synthetic alternative for the efficient synthesis of valuable molecules. In particular, C−N and C−O bonds are two important types of carbon‐heteroatom bonds. Thus, continuous efforts have been deployed to develop novel C−N/C−O bond formation methodologies involving various catalysts or promoters under TM‐free conditions, which enables the synthesis of various functional molecules comprising C−N/C−O bonds in a facile and sustainable manner. Considering the significance of C−N/C−O bond construction in organic synthesis and materials science, this review aims to comprehensively present selected examples on the construction of C−N (including amination and amidation) and C−O (including etherification and hydroxylation) bonds without transition metals. Besides, the involved promoters/catalysts, substrate scope, potential application and possible reaction mechanisms are also systematically discussed.

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“…Various amides were synthesized using MTM and isolated without the requirement of chromatography. 67 Mechanistically, silyl ester 27 is proposed to form followed by nucleophilic attack of the amine to form the amide product (Figure 23). Recently, Haas and co-workers investigated the use of polysilanes, hexamethoxydisilane 28 and dodecamethoxyneopentasilane 29 for amide bond formation and were able to synthesize different amides with low coupling reagent loading (Figure 24).…”

Section: Mukaiyamamentioning

confidence: 99%

“…Blanchet and co-workers concluded that the phenylsilane-mediated reaction does not proceed through the chemical ligation amide synthesis (i.e. intermediate 43), 79,80 but rather through a diester (67) or triester (68) formed by dehydrogenative addition of phenylsilane to the carboxylic acids (Figure 57). They were unable to isolate any reactive intermediates, and so to test this mechanistic hypothesis they explored the acetylation of morpholine with various silyl acetates (Figure 58).…”

Section: Synthesismentioning

confidence: 99%

Silyl Esters as Reactive Intermediates in Organic Synthesis

et al. 2023

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Silyl esters have been exploited as meta-stable reaction intermediates – both purposefully and unintentionally – since at least the 1960s. Their reactivity is broadly related to the substituents on the silicon, and in this way their properties can be readily modulated. Silyl esters have unique reactivity profiles that have been used to generate downstream products of a range of functionalities, and because of this many excellent methods for the synthesis of a variety of value-added chemicals have been developed. Furthermore, because of the frequent use of hydrosilanes as terminal reductants in catalytic processes, silyl ester intermediates are likely more commonly utilized by synthetic chemists than currently realized. This review comprehensively summarizes the reactions known to take advantage of reactive silyl ester intermediates and discusses examples of catalytic reactions that proceed in an unanticipated manner through silyl ester intermediates.

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Methyltrimethoxysilane (MTM) as a Reagent for Direct Amidation of Carboxylic Acids

Cited by 19 publications

References 58 publications

Functionalized Tetrazoles as Latent Active Esters in the Synthesis of Amide Bonds

Functionalized Tetrazoles as Latent Active Esters in the Synthesis of Amide Bonds

Recent Advances in Carbon‐Nitrogen/Carbon‐Oxygen Bond Formation Under Transition‐Metal‐Free Conditions

Silyl Esters as Reactive Intermediates in Organic Synthesis

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