Mechanism of thio acid/azide amidation

Journal of the American Chemical Society
Robert V KolakowskiLawrence J Williams

Abstract

A combined experimental and computational mechanistic study of amide formation from thio acids and azides is described. The data support two distinct mechanistic pathways dependent on the electronic character of the azide component. Relatively electron-rich azides undergo bimolecular coupling with thiocarboxylates via an anion-accelerated [3+2] cycloaddition to give a thiatriazoline. Highly electron-poor azides couple via bimolecular union of the terminal nitrogen of the azide with sulfur of the thiocarboxylate to give a linear adduct. Cyclization of this intermediate gives a thiatriazoline. Decomposition to amide is found to proceed via retro-[3+2] cycloaddition of the neutral thiatriazoline intermediates. Computational analysis (DFT, 6-31+G(d)) identified pathways by which both classes of azide undergo [3+2] cycloaddition with thio acid to give thiatriazoline intermediates, although these paths are higher in energy than the thiocarboxylate amidations. These studies also establish that the reaction profile of electron-poor azides is attributable to a prior capture mechanism followed by intramolecular acylation.

References

Oct 1, 1981·International Journal of Peptide and Protein Research·D Yamashiro, J Blake
Nov 4, 1994·Science·P E DawsonS B Kent
Dec 22, 1999·Current Opinion in Chemical Biology·G G Kochendoerfer, S B Kent
Feb 24, 2000·Biopolymers·J P TamZ Miao
Mar 17, 2000·Science·E Saxon, C R Bertozzi
May 18, 2000·Organic Letters·J Offer, P E Dawson
Jul 13, 2000·Organic Letters·B L NilssonR T Raines
Jul 18, 2001·Journal of the American Chemical Society·L A Marcaurelle, C R Bertozzi
Feb 6, 2003·Angewandte Chemie·Justin S MillerSamuel J Danishefsky
May 2, 2003·Journal of the American Chemical Society·Bradley L NilssonRonald T Raines
Jun 26, 2003·Journal of the American Chemical Society·Ning ShangguanLawrence J Williams
Sep 23, 2003·Angewandte Chemie·Olivier DavidJan H van Maarseveen
Mar 26, 2004·Organic Letters·Xiangming ZhuRichard R Schmidt
Jun 17, 2004·Angewandte Chemie·Maja Köhn, Rolf Breinbauer
Aug 20, 2004·Nature·Jennifer A PrescherCarolyn R Bertozzi
Oct 8, 2004·Journal of the American Chemical Society·Danica P GalonićDavid Y Gin
Jan 14, 2005·Organic Letters·Spencer Knapp, Etzer Darout
Feb 24, 2005·Journal of the American Chemical Society·Fiona L LinCarolyn R Bertozzi
Aug 16, 2005·Angewandte Chemie·Stefan BräseViktor Zimmermann
Jan 13, 2006·Nature Chemical Biology·Jennifer A Prescher, Carolyn R Bertozzi
Feb 24, 2006·Organic Letters·Kristin N BarlettLawrence J Williams

❮ Previous
Next ❯

Citations

Apr 23, 2013·Bioorganic & Medicinal Chemistry·Reda MhidiaOleg Melnyk
Apr 22, 2011·ACS Chemical Biology·Sameer S KulkarniRoman Manetsch
Aug 4, 2010·Journal of the American Chemical Society·Kalyanaraman Krishnamoorthy, Tadhg P Begley
Aug 19, 2011·Journal of the American Chemical Society·Wenting WuLanny S Liebeskind
Sep 19, 2008·Journal of the American Chemical Society·Melissa L BlackmanJoseph M Fox
Jan 24, 2012·The Journal of Organic Chemistry·Melissa L McIntoshRich G Carter
Mar 25, 2011·Organic Letters·Kaname Sasaki, David Crich
Sep 18, 2012·Organic Letters·Roberta CadoniLidia De Luca
Aug 12, 2009·Chemical Communications : Chem Comm·Paul BrearDavid R W Hodgson
Mar 29, 2014·Chemical Communications : Chem Comm·Michaela MühlbergChristian P R Hackenberger
Jan 13, 2016·The Journal of Organic Chemistry·Rajendra Shivaji Mane, Bhalchandra M Bhanage
Sep 26, 2015·Journal of Medicinal Chemistry·Wenming LiXin-Shan Ye
Nov 20, 2009·Journal of Peptide Science : an Official Publication of the European Peptide Society·Dirk T S RijkersRob M J Liskamp
Sep 25, 2015·Journal of the American Chemical Society·Andrew G RobertsSamuel J Danishefsky
Apr 4, 2015·The Journal of Organic Chemistry·Sheng XieMingdi Yan
Jun 9, 2016·The Journal of Organic Chemistry·Luana SilvaDiogo S Lüdtke
Sep 28, 2016·Chemical Reviews·Renata Marcia de FigueiredoJean-Marc Campagne
Jan 10, 2017·Chembiochem : a European Journal of Chemical Biology·Klaus VilladsenMikkel B Thygesen
Oct 29, 2015·Organic & Biomolecular Chemistry·Veladi PandurangaVommina V Sureshbabu
Mar 13, 2018·Organic & Biomolecular Chemistry·L Roopesh KumarVommina V Sureshbabu
Apr 21, 2018·Organic & Biomolecular Chemistry·Narendra NVommina V Sureshbabu
Aug 2, 2018·Organic & Biomolecular Chemistry·Yuan-Ye JiangSiwei Bi
Nov 16, 2018·Chemical Communications : Chem Comm·Julia RevueltaAlfonso Fernández-Mayoralas
Jan 12, 2019·Chemical Communications : Chem Comm·Jenna UrkowFrank Wuest
Apr 10, 2008·Chembiochem : a European Journal of Chemical Biology·Xiao-Hong TanChuan-Fa Liu
Dec 17, 2008·Angewandte Chemie·Christian P R Hackenberger, Dirk Schwarzer
Mar 24, 2010·Chemical Society Reviews·Xiangdong Hu, Roman Manetsch
May 4, 2010·Chemistry : a European Journal·Johan Hygum DamRobert Madsen
Sep 23, 2011·Organic & Biomolecular Chemistry·Vincent BouvetFrank Wuest
Apr 24, 2014·Angewandte Chemie·Jean-Simon SuppoJean-Marc Campagne
Jun 19, 2013·Chembiochem : a European Journal of Chemical Biology·Dieter Verzele, Annemieke Madder
Jan 5, 2013·Chemical Communications : Chem Comm·Sameer S KulkarniRoman Manetsch
Feb 16, 2016·Future Medicinal Chemistry·Damien BoscRebecca Deprez-Poulain
Dec 1, 2010·Chemical Communications : Chem Comm·Xiaohong ZhangChuan-Fa Liu
Sep 23, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Cheng ChenFrancis Verpoort
Sep 6, 2011·Chemical Communications : Chem Comm·Niranjan Kumar Namelikonda, Roman Manetsch
Jan 1, 2016·Chemical Science·Sheng XieMingdi Yan
Jul 28, 2015·Angewandte Chemie·Haoquan LiMatthias Beller
Sep 26, 2013·Chemical Communications : Chem Comm·Muhammad AswadYasumaru Hatanaka

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.