Phosphinmethylenderivate und Phosphinimine", Staudinger Reaction at organic-chemistry.org, https://en.wikipedia.org/w/index.php?title=Staudinger_reaction&oldid=977897474, Creative Commons Attribution-ShareAlike License, This page was last edited on 11 September 2020, at 16:57. If you do not receive an email within 10 minutes, your email address may not be registered, doi:10.1074/jbc.273.42.27668, Korth M (2010) Third-generation hydrogen-bonding corrections for semiempirical QM methods and force fields. Triphenylphosphine or tributylphosphine are most commonly used, yielding tributylphosphine oxide or triphenylphosphine oxide as a side product in addition to the desired amine. doi:10.1039/C3RA46594B, Thordarson P (2011) Determining association constants from titration experiments in supramolecular chemistry. doi:10.1016/j.bmcl.2003.10.059, Zhen P-W, Xie X-M, Wang W, Wang X-J, Guo Y-P, Tu Q-D (2006) Reduction of azide to amine using Fe/AlCl3 or Fe/BiCl3 system in aqueous EtOH. We wish to thank CONACYT (SEP-82585) and UASLP (C11-FRC-09-37.7) for their financial support. J Am Chem Soc 134:71–74. 71, 939–947 (2017). J Am Chem Soc 124:10887–10893. doi:10.1021/ja00082a011, Glushkov RG, Dronova LN, Elina AS, Porokhovaya MV, Padeiskaya EN, Radkevich TP, Shipilnova LD (1990) Synthesis and biological examination of tricyclic analogs of oxolinic acid. Tetrahedron Lett 49:6759–6761. doi:10.1016/j.tet.2006.11.079, Leyva E, de Loera D, Leyva S (2008) Photochemistry of 7-azide-1-ethyl-3-carboxylate-6,8-difluoroquinolone: a novel reagent for photoaffinity labeling. A theoretical study. A selective and facile method allows the reduction of aromatic azides to amines by employing borontrifluoride diethyl etherate and sodium iodide. Pap. Pharm Chem J 24:43–47. RSC Adv 4:5660–5665. J Am Chem Soc 116:909–915. Azides are easily reduced amines by LiAlH4, NaBH4, NaBH4/LiCl, NaBH4/CoCl2/H2O, NaBH4/ZrCl4,Pd/C and H2, Mg or Ca in MeOH, Ni raney. doi:10.1016/j.tetlet.2008.07.156, Mafra L, Santos SM, Siegel R, Alves I, Almeida-Paz FA, Dudenko D, Spiess HW (2012) Packing interactions in hydrated and anhydrous forms of the antibiotic ciprofloxacin: a solid-state NMR, X-ray diffraction, and computer simulation study. O system by crystal structure correlation methods. Reduction of Amides (for more detail see Chapter 22) Reactions usually in Et 2 O or THF followed by H 3 O + work-ups . doi:10.1039/C0CS00062K, Vega-Rodríguez S, Jiménez-Cataño R, Leyva E, Loredo-Carrillo SE (2013) Intramolecular hydrogen bonds in fluorinated, methoxylated, or unsubstituted 2-(anilino)-1,4-naphthoquinones.  The reaction follows this stoichiometry: The Staudinger reduction is conducted in two steps. doi:10.1021/cr030101q, MOPAC2009, Stewart, J.J.P, Stewart Computational Chemistry, Version 11.366 W. web: http://OpenMOPAC.net, Naeem A, Badshah SL, Muska M, Ahmad N, Khan K (2016) The current case of quinolones: synthetic approaches and antibacterial activity. doi:10.1021/bi00435a039, Sinnokrot MO, Valeev EF, Sherrill CD (2002) Estimates of the Ab initio limit for π–π interactions: the benzene dimer. doi:10.1021/ja025896h, Soni K (2012) Fluoroquinolones: chemistry & action. doi:10.1021/ja208647n, Mitscher LA (2005) Bacterial topoisomerase inhibitors: quinolone and pyridone antibacterial agents. The Mechanism of Amide Reduction by LiAlH 4 Primary and secondary amides have a proton connected to the nitrogen that is acidic enough to be attacked by the hydride. IBSN: 978-0-470-87171-3, Hermecz I, Vasvári-Debreczy L, Podányi B, Kereszturi G, Balogh M, Horváth A, Várkonyi P (1998) Regioselective nucleophilic substitution of halogen derivatives of 1-substituted 4-oxo-1,4-dihydroquinoline-3-carboxylic acids. doi:10.3987/COM-98-8143, Khodursky AB, Cozzarelli NR (1998) The mechanism of inhibition of topoisomerase IV by quinolone antibacterials. Heterocycles 48:1111–1116. J Biol Chem 273:27668–27677. 6H2O or Fe/BiCl3 system in H2O/ethanol (2:1, V:V) at room temperature.  In aqueous media, the aza-ylide intermediate rearranges, to produce an amide linkage and the phosphine oxide, and is so named the Staudinger ligation because it ligates two molecules together, whereas in the classical Staudinger reaction, the two products are not covalently linked after hydrolysis. doi:10.1002/cjoc.200690157. Manuel Nava 6, Zona Universitaria, San Luis Potosí, SLP, 78210, Mexico, Socorro Leyva-Ramos, Rogelio Jiménez-Cataño & Sarai Vega-Rodríguez, Unidad Académica de Ciencias Químicas, Universidad Autónoma de Zacatecas, Carretera Zacatecas-Guadalajara Km 6, Ejido la Escondida s/n, Edificio 6, Zacatecas, Zac, 98136, Mexico, Instituto de Investigaciones Químico Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Edificio B-1, Ciudad Universitaria, Morelia, Mich, 58066, Mexico, You can also search for this author in Tetrahedron 63:2093–2097. Bioorg Med Chem Lett 15:4247–4251. 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. We have found that the yields of the amine obtained by catalytic hydrogenation are, in some cases, low or variable, and the products are difficult to purify'. Enter your email address below and we will send you your username, If the address matches an existing account you will receive an email with instructions to retrieve your username, I have read and accept the Wiley Online Library Terms and Conditions of Use. - 220.127.116.11. doi:10.1007/s00894-007-0233-4, Tapia-Juárez M, González-Campos JB, Contreras-Celedón C, Corona D, Cuevas-Yañez E, Chacón-García L (2014) A new type of anion receptor: pyrrolyl quinones. Of interest in chemical biology research, the Staudinger ligation is a modification of the classical Staudinger reaction in which an electrophilic trap (usually a methyl ester) is placed on the triaryl phosphine. Acc Chem Res 35:887–894. The intermediate, e.g. 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. , In one application this reaction is used to create a bond between a nucleoside and a fluorescent marker:, The Staudinger ligation is used to site-specifically incorporate organic molecules (such as fluorescent dyes) into recombinant polypeptides containing unnatural azide-conjugated aminoacids (incorporated, for instance, via suppression of the amber stop codon: https://pubs.acs.org/doi/pdf/10.1021/ja027007w), For the reaction between imines and ketenes to form, https://pubs.acs.org/doi/pdf/10.1021/ja027007w, "Über neue organische Phosphorverbindungen III. Chem Soc Rev 40:1305–1323. Unlimited viewing of the article PDF and any associated supplements and figures. Cryst Growth Des 13:1050–1058. and you may need to create a new Wiley Online Library account. doi:10.10213390/molecules21040268, Richter SN, Gatto B, Tabarrini O, Fravolini A, Palumbo M (2005) Antiviral 6-amino-quinolones: molecular basis for potency and selectivity. Chem Rev 105:559–592. Summary. https://doi.org/10.1007/s11696-016-0016-4, DOI: https://doi.org/10.1007/s11696-016-0016-4, Over 10 million scientific documents at your fingertips, Not logged in Below is the link to the electronic supplementary material. doi:10.1515/znb-2007-0807, Zhang Z, Zhou W, Yu A (2004) Synthesis and antibacterial activity of 7-(substituted)aminomethyl quinolones. Socorro Leyva-Ramos. Unlimited viewing of the article/chapter PDF and any associated supplements and figures. Facultad de Ciencias Químicas, Universidad Autónoma de San Luis Potosí, Av. Zeitschrift für Naturforschung B 62:1045–1051. PubMed Google Scholar. 6H 2 O or Fe/BiCl 3 system in H 2 O/ethanol (2:1, V:V) at room temperature.Fifteen azides with different functional groups were well reduced to the corresponding amines in excellent yields. Bioorg Med Chem Lett 14:393–395. Biochemistry 28:3886–3894. The Staudinger reaction is a chemical reaction of an azide with a phosphine or phosphite produces an iminophosphorane. doi:10.1021/cg301299e, Zahra JA, Khanfar MA, El-Abadelah MM, Abu Thaher BA, El-Abadla NS, Voelter WZ (2007) Synthesis of some ethyl 3-(aryldiazenyl)-7-oxo-dihydropyrido[2,3-f]quinoxaline-8-carboxylates. a given acyl azide is heated and then hydrolyzed. Amides, RCONR' 2, can be reduced to the amine, RCH 2 NR' 2 by conversion of the C=O to -CH 2- Amides can be reduced by LiAlH 4 but NOT the less reactive NaBH 4 https://doi.org/10.1007/s11696-016-0016-4. Part of Springer Nature. Wiley, England, pp 155–536. An efficient reduction of azide to amine: a new methodology to synthesize ethyl 7-amino-1-ethyl-6,8-difluoroquinolone-3-carboxylate and its spectroscopic characterization. doi:10.1016/j.jfluchem.2012.10.001, Vitorino GP, Sperandeo NR, Caira MR, Mazzieri MR (2013) A supramolecular assembly formed by heteroassociation of ciprofloxacin and norfloxacin in the solid state: co-crystal synthesis and characterization. J Fluor Chem 145:58–62. First phosphine imine-forming reaction is conducted involving treatment of the azide with the phosphine. Chem. First phosphine imine-forming reaction is conducted involving treatment of the azide with the phosphine. FT-IR and H1 NMR spectra of the final product, ethyl 7-amino-1-ethyl-6,8-difluoroquinolone-3-carboxylate, suggests the formation of dimers, a feature already observed in norfloxacin. There are a lot of conditions, please check this book: This attracted our attention to synthesize a 7-azide-fluoroquinolone, which could be converted to amine performing a photochemical reaction using CuI as catalyst. An expeditious synthesis of novel fluoroquinolone derivatives. The Staudinger reduction is conducted in two steps. doi:10.1016/j.bmcl.2005.06.074, Shen LL, Mitscher LA, Sharma PN, O’Donnell TJ, Chu DTW, Cooper CS, Rosen T, Pernet AG (1989) Mechanism of inhibition of DNA gyrase by quinolone antibacterials: a cooperative drug-DNA binding model. J Mol Model 13:1173–1213. Rappoport Z (ed) Synthesis of anilines. doi:10.1007/BF00769385, Hartwing JF, Shekhar S, Shen Q, Barrios-Landeros F (2007) The chemistry of anilines. Indo Global J Pharm Sci 2:43–53. J Chem Theory Comput 6:3808–3816. © 2020 Springer Nature Switzerland AG. The iminophosphorane is then hydrolyzed in the second step to the amine and a phosphine oxide byproduct. A traceless version of the reaction leaves behind no residual atoms and has been used to ligate peptides. Please check your email for instructions on resetting your password. Chin J Chem 24:825–826. An example of a Staudinger reduction is the organic synthesis of this pinwheel compound:. 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. Staudinger reduction. The intermediate, e.g. The full text of this article hosted at iucr.org is unavailable due to technical difficulties. Correspondence to View the article PDF and any associated supplements and figures for a period of 48 hours. Reaction type: Nucleophilic Acyl Substitution then Nucleophilic Addition. doi:10.1021/ar020003b, Leyva S, Leyva E (2007) Thermochemical reaction of 7-azido-1-ethyl-6,8-difluoroquinolone-3-carboxylate with heterocyclic amines. This step occurs before the nucleophilic addition of the hydride ion: identify the starting material, the other reagents, or both, needed to synthesize a given amine by any of the routes listed in Objective 1. write a general equation to illustrate the preparation of an arylamine by the reduction of a nitro compound, and balance such an equation. ISSN: 2249-1023, Stewart JJP (2007) Optimization of parameters for semiempirical methods V: modification of NDDO approximations and application to 70 elements. Leyva-Ramos, S., Hernández-López, H., Jiménez-Cataño, R. et al. doi:10.1021/ct100408b, Kovács A, Szabó A, Hargittai I (2002) Structural characteristics of intramolecular hydrogen bonding in benzene derivatives.