https://doi.org/10.1021/ja203661j, Liu C, Baumann H (2002) Exclusive and complete introduction of amino groups and their N-sulfo and N-carboxymethyl groups into the 6-position of cellulose without the use of protecting groups. https://doi.org/10.1002/actp.1997.010480801, Konigsberg W (1972) [13] Reduction of disulfide bonds in proteins with dithiothreitol. This methodology has been applied towards the preparation of biologically important imine-containing pyrrolobenzodiazepines and their dilactams through an intramolecular reductive-cyclization process. triphenylphosphine phenylimide, is then subjected to hydrolysis to produce a phosphine oxide and an amine: The overall conversion is a mild method of reducing an azide to an amine. https://doi.org/10.1002/masy.200950609, Rinaudo M, Pavlov G, Desbrières J (1999) Influence of acetic acid concentration on the solubilization of chitosan. A traceless version of the reaction leaves behind no residual atoms and has been used to ligate peptides. https://doi.org/10.1021/bm2017004, Fox SC, Li B, Xu D, Edgar KJ (2011) Regioselective esterification and etherification of cellulose: a review. Reductions with hydrosilanes has only specialized applications. The azide group is usually reduced to the amino function by catalytic reduction (using Raney nickel, palladium, etc) or by treatment with lithium aluminium hydride. Prog Polym Sci 53:52–85. PubMed Google Scholar. Prog Polym Sci 26:1605–1688. https://doi.org/10.1021/ja805044x, Pereira JM, Edgar KJ (2014) Regioselective synthesis of 6-amino-and 6-amido-6-deoxypullulans. https://doi.org/10.1016/J.CARBPOL.2014.01.045, Zhang R, Edgar KJ (2015) Water-soluble aminocurdlan derivatives by chemoselective azide reduction using NaBH4. Carbohydr Polym 162:1–9. Carbohydr Res 230:165–177. Biomacromol 14:1388–1394. https://doi.org/10.1002/anie.200904168, Daly WH, Lee S (1989) Peptide graft copolymers from soluble aminodeoxycellulose acetate. https://doi.org/10.1016/J.CARBPOL.2017.01.008, Liu S, Gao C, Mosquera-Giraldo LI et al (2018) Selective synthesis of curdlan ω-carboxyamides by Staudinger ylide nucleophilic ring-opening. The mechanism begins with attack of the phos-phorus on the far nitrogen of the organic azide to give a phosphazide intermediate. Biomacromol 10:11. https://doi.org/10.1021/acs.biomac.8b01150, CAS  Part of Springer Nature. Hofmann or Curtius rearrangements. Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. The intermediate, e.g. J Am Chem Soc 125:7754–7755. They typically involve a three-step reaction sequence: introducing a leaving group, azide displacement of that leaving group, and azide reduction to amine or amide. Learn more about Institutional subscriptions, Baker ND, Griffin RJ, Irwin WJ, Slack JA (1989) The reduction of aryl azides by dithiothreitol: a model for bioreduction of aromatic azido-substituted drugs. Springer, Boston, pp 147–160, Liebert T, Hussain MA, Heinze T (2005) Structure determination of cellulose esters via subsequent functionalization and NMR spectroscopy. Carbohydr Polym 122:84–92. nucleophilic attack by an azide ion on an alkyl halide, followed by reduction of the azide so formed. https://doi.org/10.1021/bm400041w. We thank the Institute for Critical Technology and Applied Science (ICTAS), the Macromolecules Innovation Institute (MII), and the Virginia Tech Departments of Sustainable Biomaterials and of Chemistry for their financial, facilities, and educational support. https://doi.org/10.1007/s10719-007-9039-y, Matsui Y, Ishikawa J, Kamitakahara H et al (2005) Facile synthesis of 6-amino-6-deoxycellulose. https://doi.org/10.1080/10426500490466544, Klemm D, Heinze T, Philipp B, Wagenknecht W (1997) New approaches to advanced polymers by selective cellulose functionalization. Phosphorus, Sulfur Silicon Relat Elem 179:1813–1817. Correspondence to Phosphinmethylenderivate und Phosphinimine. Polym Chem 7:3848–3856. https://doi.org/10.1016/J.EJPB.2012.04.007, Article  Department of Chemistry, Virginia Tech, Blacksburg, VA, 24061, USA, Department of Biochemistry, Virginia Tech, Blacksburg, VA, 24061, USA, Macromolecules Innovation Institute, Virginia Tech, Blacksburg, VA, 24061, USA, Department of Sustainable Biomaterials, Virginia Tech, Blacksburg, VA, 24061, USA, You can also search for this author in https://doi.org/10.1016/J.BMC.2005.11.013, Jacobs S, Cuatrecasas P (1980) Disulfide reduction converts the insulin receptor of human placenta to a low affinity form. The reduction system must be chosen by taking into account the substitution pattern of substrates. Macromol Symp 280:72–85. 6-amino-6-deoxyamylose. Gao, C., Fisher, Z.B. First phosphine imine-forming reaction is conducted involving treatment of the azide with the phosphine. Agric Biol Chem 40:2501–2502. This intermediate then goes through a rearrangement that releases a molecule of nitrogen gas and forms a N-P ylide. Angew Chem Int Ed 48:8896–8899. Anstelle des Triphenylphosphans kann nahezu jedes andere organische Phosphan verwendet werden.[5]. As there are a variety of methods for preparing azides readily, the Staudinger Reaction makes it possible to use - N 3 as an - NH 2 … PubMed  Org Process Res Dev 10:846. https://doi.org/10.1021/OP060109C, Yang YY, Ficht S, Brik A, Wong CH (2007) Sugar-assisted ligation in glycoprotein synthesis. Cellulose The iminophosphorane is then hydrolyzed in the second step to the amine and a phosphine oxide byproduct. Die Staudinger-Reaktion ist eine milde Alternative zu anderen Aminsynthesen, z. Macromol Rapid Commun 27:208–213. Chem Commun 50:4603. https://doi.org/10.1039/c4cc00774c, Ning S, Sreenivas K, Rachel G, Lawrence WJ (2003) The reaction of thio acids with azides: a new mechanism and new synthetic applications. https://doi.org/10.1016/S0079-6700(01)00027-2, Fox SC, Edgar KJ (2012) Staudinger reduction chemistry of cellulose: synthesis of selectively O-acylated 6-amino-6-deoxy-cellulose. Amino and amido polysaccharides include some of the most complex, fascinating natural polymers, due in part to their important biological activities and intriguing biomedical applications. [5], Beim Rest R des Azids handelt es sich meist um einen Alkyl- oder Arylrest. For example, azide (67) was converted into the amine (68) by treatment with SnCl 2 in MeOH (64% yield), whereas catalytic hydrogenation or LiAlH 4 reduction could not be used due to loss of the 5-bromo group. https://doi.org/10.1039/C6PY00539J, Mühlberg M, Siebertz KD, Schlegel B et al (2014) Controlled thioamide vs. amide formation in the thioacid–azide reaction under acidic aqueous conditions. https://doi.org/10.1016/J.CARRES.2005.02.030, Meng X, Edgar KJ (2016) “Click” reactions in polysaccharide modification. Der Reaktionsmechanismus der Staudinger-Reaktion ist nicht vollständig geklärt. The mechanism begins with attack of the phos-phorus on the far nitrogen of the organic azide to give a phosphazide intermediate. Carbohydr Res 337:1297–1307. In this study, we describe an efficient approach to selectively reduce polysaccharide azides to amines, employing 1,4-dithiothreitol (DTT). Azide reduction by DTT or thioacetic acid provides access to amino and amido polysaccharides. triphenylphosphine phenylimide, is then subjected to hydrolysis to produce a phosphine oxide and an amine: R 3 P=NR' + H 2 O → R 3 P=O + R'NH 2. [3], Der Reaktionsmechanismus der Staudinger-Reaktion ist nicht vollständig geklärt. We further report a new approach to reduce polysaccharide azides directly to acetamides using thioacetic acid, with high conversion, without going through the free amine intermediate. Carbohydr Res 306:427–433, Ochiai H, Huang W, Wang L-X (2008) Expeditious chemoenzymatic synthesis of homogeneous N-glycoproteins carrying defined oligosaccharide ligands. Staudinger reduction. - 91.121.79.58. [4] Die Staudinger-Reaktion beginnt mit dem nukleophilen Angriff von Triphenylphosphan am eingesetzten Azid 1. Proteinligation ist als Staudinger-Ligation bekannt. The reaction mechanism centers around the formation of an iminophosphorane through nucleophilic addition of the aryl or alkyl phosphine at the terminal nitrogen atom of the organic azide and expulsion of diatomic nitrogen. https://doi.org/10.1016/S0008-6215(02)00132-5, Liu S, Edgar KJ (2015) Staudinger reactions for selective functionalization of polysaccharides: a review. The LibreTexts libraries are Powered by MindTouch ® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. Kevin J. Edgar. https://doi.org/10.1021/jacs.5b10675, Article  https://doi.org/10.1016/S0076-6879(72)25015-7, Köwitsch A, Zhou G, Groth T (2018) Medical application of glycosaminoglycans: a review. © 2020 Springer Nature Switzerland AG. https://doi.org/10.1016/J.CARBPOL.2018.02.074, Madhunapantula SV, Achur RN, Bhavanandan VP, Gowda DC (2007) The effect of substitution of the N-acetyl groups of N-acetylgalactosamine residues in chondroitin sulfate on its degradation by chondroitinase ABC.