Thio Acid/Azide Amidation:  An Improved Route to <i>N</i>-Acyl Sulfonamides

Barlett, Kristin N.; Kolakowski, Robert V.; Katukojvala, Sreenivas; Williams, Lawrence J.

doi:10.1021/ol052671d

Cited by 61 publications

(31 citation statements)

References 23 publications

(23 reference statements)

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“…Lupton rationalized that an appropriately positioned electron-withdrawing group would promote fragmentation by stabilizing developing negative charge in the transition state. It was thus found that cyclic α-iodomethyl-β-keto esters of various ring sizes undergo nucleophile-triggered fragmentation (equation 22). 25 The researchers propose a concerted fragmentation process, as opposed to a stepwise retro-Dieckmann and elimination sequence, based on the combined weight of two kinetic observations: (1) Cyclopentanones fragment faster than cyclohexanones or cycloheptanones, consistent with the ring opening being part of the rate-determining step.…”

Section: Fragmentation Of Acyclic Substratesmentioning

confidence: 99%

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6.19 Fragmentation Reactions

Hoang

Dudley

Williams

2014

Comprehensive Organic Synthesis II

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Section: Fragmentation Of Acyclic Substratesmentioning

confidence: 99%

“…Fragmentative cleavage of a trimethylsilylethyl sulfonamide plays a supporting role in amidation methodology based on sulfonyl azide chemistry from the Williams laboratory (equation19) 22. …”

mentioning

confidence: 99%

6.19 Fragmentation Reactions

Hoang

Dudley

Williams

2014

Comprehensive Organic Synthesis II

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“…[175] Auf der Grundlage dieser Reaktion wurden außerdem potenzielle chemoselektive Ligationen von Sulfonamidderivaten entwickelt, obgleich die Anwendung zur Ligation längerer Peptide noch aussteht. [176] rung der a-Ketosäuren auftritt. Entscheidend an dieser Reaktion ist aber, dass ungeschützte Peptide mit Lys-und Asp- [176] sowie Trp-, Tyr-und Arg-Bausteinen [177] verknüpft werden können, wie mit der Synthese des Hexapeptids 135 demonstriert wurde (Schema 24 B).…”

Section: Spurlose Staudinger-ligationunclassified

“…[176] rung der a-Ketosäuren auftritt. Entscheidend an dieser Reaktion ist aber, dass ungeschützte Peptide mit Lys-und Asp- [176] sowie Trp-, Tyr-und Arg-Bausteinen [177] verknüpft werden können, wie mit der Synthese des Hexapeptids 135 demonstriert wurde (Schema 24 B). Mögliche Ligationsstellen schließen dabei Phe-Ala, Pro-Ala, Val-Gly und Ala-Ala ein.…”

Section: Spurlose Staudinger-ligationunclassified

Chemoselektive Ligations‐ und Modifikationsstrategien für Peptide und Proteine

2008

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Die Untersuchung biologischer Fragestellungen mit chemischen Methoden wird meist als “Chemische Biologie” bezeichnet und setzt voraus, dass biologisch relevante Makromoleküle, wie Peptide und Proteine, chemisch zugänglich sind. Auf der Festphasensynthese von Peptiden aufbauend wurden viele chemoselektive Ligations‐ und Modifikationstechniken zur Verknüpfung synthetischer Peptide oder funktionaler Einheiten zu größeren synthetischen, biologisch relevanten Makromolekülen entwickelt. Dieser Aufsatz fasst die aktuellen Entwicklungen auf dem Gebiet der chemoselektiven Ligations‐ und Modifikationsstrategien zusammen und illustriert ihre Anwendbarkeit an Beispielen aus der chemischen Totalsynthese von Proteinen bis hin zur Semisynthese natürlicher modifizierter Proteine.

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“…Due to their nucleophilicity, thioacids have found broad applications, for instance the synthesis of thiols and thioesters1 as well as in reactions with azides and nitrosulfonamides 2,3. The recognition that thioacids are not only exploitable nucleophiles, but also can function as overall acylating agents under mild conditions, has enabled the development of a number of new methods for the construction of simple amides, as well as amide bonds in the context of peptide ligations 4…”

mentioning

confidence: 99%

A simple method for the conversion of carboxylic acids into thioacids with Lawesson’s reagent

Rao

Nagorny

et al. 2009

Tetrahedron Letters

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A one-step protocol for the conversion of carboxylic acids to thioesters, using Lawesson's Reagent, has been developed.Thioacids represent a well-established and versatile class of organic compounds. Due to their nucleophilicity, thioacids have found broad applications, for instance the synthesis of thiols and thioesters 1 as well as in reactions with azides and nitrosulfonamides. 2,3 The recognition that thioacids are not only exploitable nucleophiles, but also can function as overall acylating agents under mild conditions, has enabled the development of a number of new methods for the construction of simple amides, as well as amide bonds in the context of peptide ligations. 4In the course of a current program directed toward the synthesis of glycopeptides (and glycoproteins), 5 we recently disclosed several strategies which use thioacids as the coupling partners.6 The value of such methods depends on the accessibility of the thioacids. We have now directed our efforts to the development of a new and practical protocol for the selective installation of thioacid functionality.Among the current methods for synthesizing thioacids, three are most commonly used. One involves pre-formation of activated carboxylic acids, which are converted to thioacids by reaction with hydrosulfide (HS) anion. Another involves prior coupling of the carboxylic acid with either HSFmoc, HSTrt or HSTmob. Removal of the protecting group releases the target thioacid. 8 Finally, Boc solid phase peptide synthesis (SPPS) with a thioester solid support can be applied to the preparation of large peptide thioacids.9 The major limitations of these approaches include the toxicity of H 2 S, required recourse to activating agents, current commercial unavailability of HSFmoc and HSTmob, and the inconvenience factors associated with a multistep protocol to accomplish a simple -OH to -SH interconversion. We describe herein the development of a new and efficient one-step synthesis of thioacids from the corresponding carboxylic acids, using Lawesson's Reagent (LR).Lawesson's Reagent is commercially available, inexpensive, and widely used in organic synthesis, particularly for the transformation of a carbonyl functional group to its thiocarbonyl Correspondence to: Samuel J Danishefsky. Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. 10 Remarkably, there had been no systematic study investigating the preparation of thioacids by direct reaction between carboxylic acid and LR. As outlined in Scheme 1, we postulated that, perhaps, a carboxylic acid (1) could react with LR in a manner analogous to that observe...

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Thio Acid/Azide Amidation: An Improved Route to N-Acyl Sulfonamides

Cited by 61 publications

References 23 publications

6.19 Fragmentation Reactions

6.19 Fragmentation Reactions

Chemoselektive Ligations‐ und Modifikationsstrategien für Peptide und Proteine

A simple method for the conversion of carboxylic acids into thioacids with Lawesson’s reagent

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