A catalytic one-step synthesis of peptide thioacids: the synthesis of leuprorelin <i>via</i> iterative peptide–fragment coupling reactions

Matsumoto, Takuya; Sasamoto, Koki; Hirano, Ryo; Oisaki, Kounosuke; Kanai, Motomu

doi:10.1039/c8cc07935h

Cited by 8 publications

(5 citation statements)

References 47 publications

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“…Notably, the preliminary demonstration of the iterative formation of amide bonds (Scheme ) represents a novel strategy for the iterative synthesis of bulky peptides. This elongation in the N → C direction is complementary to the conventional methods that rely on N -terminal ligation . Further studies to expand the reaction scope of this methodology and its application to the synthesis of more diverse peptide structures are currently in progress in our laboratory.…”

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confidence: 99%

Radical-Mediated Activation of Esters with a Copper/Selectfluor System: Synthesis of Bulky Amides and Peptides

2021

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Herein, we describe a new approach for the activation of esters via a radical-mediated process enabled by a copper/Selectfluor system. A variety of para-methoxybenzyl esters derived from bulky carboxylic acids and amino acids can be easily converted into the corresponding acyl fluorides, directly used in the one-pot synthesis of amides and peptides. As a proof of concept, this method was applied to the iterative formation of sterically hindered amide bonds.

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Radical-Mediated Activation of Esters with a Copper/Selectfluor System: Synthesis of Bulky Amides and Peptides

2021

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“…Interestingly,e lectron-poor nitro group containing thioacid C9 required extended reaction time to furnish as malla mount of thioester D9.T he use of thioacids and the salts thereof have attracted increasing attention of late within the field of peptidea nd protein chemistry. [63][64][65][66][67][68] To our delight, amino acid derived thioacid C10 furnishedh ydrothiolation product D10 in 59 %y ield, without any deprotection of the amine being observed, highlighting the potentialu se of this methodology fort he functionalization of peptides.…”

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confidence: 99%

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

McCourt

Scanlan

2020

Chemistry A European J

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Am ild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. Av ariety of sulfur containingm otifs including alkanethiols,t hiophenols and thioacidsu ndergo an atmospheric oxygen-mediated radicalh ydrothiolation reaction with ap lethora of alkenes in good yield with excellent functional group compatibility,t ypically with short reaction times to furnisharange of functionalized products. Biomoleculesp rovedt olerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds throughr adical intermediates in at hiol-ene reaction manifold. Them ethodology offers an efficient "green" approach for thiol-ene mediated "click" ligation and am ilder alternative to thermally initiated hydrothiolation processes.

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“…Amide bond formation using PTC under various conditions has been reported [34][35][36][37][38][39][40][41][42][43] , but PTCs have never been used in iterative N-to-C peptide synthesis. Based on our previous development of a general, one-step PTC synthesis from peptides using a catalytic diacetyl sulfide (Ac 2 S) and potassium thioacetate (AcSK) 44 , we envisioned the scheme shown in Fig. 1b.…”

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confidence: 99%

Practical N-to-C peptide synthesis with minimal protecting groups

Tatsumi,

Sasamoto,

Matsumoto

et al. 2023

Commun Chem

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Accessible drug modalities have continued to increase in number in recent years. Peptides play a central role as pharmaceuticals and biomaterials in these new drug modalities. Although traditional peptide synthesis using chain-elongation from C- to N-terminus is reliable, it produces large quantities of chemical waste derived from protecting groups and condensation reagents, which place a heavy burden on the environment. Here we report an alternative N-to-C elongation strategy utilizing catalytic peptide thioacid formation and oxidative peptide bond formation with main chain-unprotected amino acids under aerobic conditions. This method is applicable to both iterative peptide couplings and convergent fragment couplings without requiring elaborate condensation reagents and protecting group manipulations. A recyclable N-hydroxy pyridone additive effectively suppresses epimerization at the elongating chain. We demonstrate the practicality of this method by showcasing a straightforward synthesis of the nonapeptide DSIP. This method further opens the door to clean and atom-efficient peptide synthesis.

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A catalytic one-step synthesis of peptide thioacids: the synthesis of leuprorelin via iterative peptide–fragment coupling reactions

Abstract: A catalytic one-step synthesis of peptide thioacids with suppressed epimerization was developed and applied to an iterative fragment coupling protocol.

Cited by 8 publications

References 47 publications

Radical-Mediated Activation of Esters with a Copper/Selectfluor System: Synthesis of Bulky Amides and Peptides

Radical-Mediated Activation of Esters with a Copper/Selectfluor System: Synthesis of Bulky Amides and Peptides

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

Practical N-to-C peptide synthesis with minimal protecting groups

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