Abstract
Organic azides are among the most important structural classes of chemical substances, which are applied to organic synthesis, chemical biology, and materials science. Thus, there is continuing interest in the development of novel methods for the incorporation of a N3 group into organic molecules. Recently, direct C–H and C–C bond azidation have emerged as a straightforward and atom-economic strategy for C–N3 bond formation. This chapter highlights recent advances in this fast growing research area and also includes important pioneering studies in this area.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Pinho e Melo TMVD (2010) Synthesis of azides. In: Bräse S, Banert K (eds) Organic azides: syntheses and applications. Wiley-VCH, pp 53–94
Bräse S, Gil C, Knepper K, Zimmermann V (2005) Organic azides: an exploding diversity of a unique class of compounds. Angew Chem Int Ed 44(33):5188–5240
Bräse S, Banert K (2010) Organic azides. Wiley-VCH, Weinheim
Jung N, Bräse S (2012) Vinyl and alkynyl azides: well-known intermediates in the focus of modern synthetic methods. Angew Chem Int Ed 51(49):12169–12171
Thirumurugan P, Matosiuk D, Jozwiak K (2013) Click chemistry for drug development and diverse chemical‐biology applications. Chem Rev 113(7):4905–4979
Huryn DM, Okabe M (1992) AIDS-driven nucleoside chemistry. Chem Rev 92(8):1745–1768
Minozzi M, Nanni D, Spagnolo P (2009) From azides to nitrogen-centered radicals: applications of azide radical chemistry to organic synthesis. Chem Eur J 15(32):7830–7840
Lapointe G, Kapat A, Weidner K, Renaud P (2012) Radical azidation reactions and their application in the synthesis of alkaloids. Pure Appl Chem 84(7):1633–1641
Chiba S (2012) Application of organic azides for the synthesis of nitrogen-containing molecules. Synlett 23:21–44
Scriven EFV, Turnbull K (1988) Azides: their preparation and synthetic uses. Chem Rev 88(2):297–368
Driver TG (2010) Recent advances in transition metal-catalyzed N-atom transfer reactions of azides. Org Biomol Chem 8(17):3831–3846
Kumar R, Wiebe LI, Knaus EE (1993) Synthesis and antiviral activity of novel 5-(1-azido-2-haloethyl) and 5-(1-azido-, amino-, or methoxyethyl) analogs of 2′-deoxyuridine. J Med Chem 36(17):2470–2474
Chen L, Zhang Y, Ding G, Ba M, Guo Y, Zou Z (2013) Two new derivatives of 2, 5-dihydroxyphenylacetic acid from the kernel of entada phaseoloides. Molecules 18(2):1477–1482
Chemler SR, Bovino MT (2013) Catalytic aminohalogenation of alkenes and alkynes. ACS Catal 3(6):1076–1091
McDonald RI, Liu G, Stahl SS (2011) Palladium(II)-catalyzed alkene functionalization via nucleopalladation: stereochemical pathways and enantioselective catalytic applications. Chem Rev 111(4):2981–3019
Jensen KH, Sigman MS (2008) Mechanistic approaches to palladium-catalyzed alkene difunctionalization reactions. Org Biomol Chem 6(22):4083–4088
Besset T, Poisson T, Pannecoucke X (2015) Direct vicinal difunctionalization of alkynes: an efficient approach towards the synthesis of highly functionalized fluorinated alkenes. Eur J Org Chem 13:2765–2789
Romero RM, Wöste TH, Muñiz K (2014) Vicinal difunctionalization of alkenes with iodine(III) reagents and catalysts. Chem Asian J 9(4):972–983
Denmark SE, Kuester WE, Burk MT (2012) Catalytic, asymmetric halofunctionalization of alkenes—a critical perspective. Angew Chem Int Ed 51(44):10938–10953
Li G, Kotti SRSS, Timmons C (2007) Recent development of regio- and stereoselective aminohalogenation reaction of alkenes. Eur J Org Chem 17:2745–2758
Jong SD, Nosal DG, Wardrop DJ (2012) Methods for direct alkene diamination, new & old. Tetrahedron 68(22):4067–4105
Kapat A, König A, Montermini F, Renaud P (2011) A radical procedure for the anti-markovnikov hydroazidation of alkenes. J Am Chem Soc 133(35):13890–13893
Leggans EK, Barker TJ, Duncan KK, Boger DL (2012) Iron(III)/NaBH4-mediated additions to unactivated alkenes: synthesis of novel 20′-vinblastine analogues. Org Lett 14(6):1428–1431
Guerin DJ, Horstmann TE, Miller SJ (1999) Amine-catalyzed addition of azide ion to α, β-unsaturated carbonyl compounds. Org Lett 1(7):1107–1109
Waser J, Nambu H, Carreira EM (2005) Cobalt-catalyzed hydroazidation of olefins: convenient access to alkyl azides. J Am Chem Soc 127(23):8294–8295
Shyam PK, Jang HY (2014) Metal–organocatalytic tandem azide addition/oxyamination of aldehydes for the enantioselective synthesis of β-amino α-hydroxy esters. Eur J Org Chem 9:1817–1822
Matcha K, Narayan R, Antonchick AP (2013) Metal-free radical azidoarylation of alkenes: rapid access to oxindoles by cascade C–N and C–C bond-forming reactions. Angew Chem Int Ed 52(31):7985–7989
Nocquet-Thibault S, Rayar A, Retailleau P, Cariou K, Dodd RH (2015) Iodine(III)-mediated diazidation and azido-oxyamination of enamides. Chem Eur J 21(40):14205–14210
Yuan YA, Lu DF, Chen YR, Xu H (2016) Iron-catalyzed direct diazidation for a broad range of olefins. Angew Chem Int Ed 55(2):534–538
Lu MZ, Wang CQ, Loh TP (2015) Copper-catalyzed vicinal oxyazidation and diazidation of styrenes under mild conditions: access to alkyl azides. Org Lett 17(24):6110–6113
Valiulin RA, Mamidyala S, Finn FG (2015) Taming chlorine azide: access to 1,2-azidochlorides from alkenes. J Org Chem 80(5):2740–2755
Xu L, Mou XQ, Chen ZM, Wang SH (2014) Copper-catalyzed intermolecular azidocyanation of aryl alkenes. Chem Commun 50:10676–10679
Prasad PK, Reddi RN, Sudalai A (2015) Oxidant controlled regio- and stereodivergent azidohydroxylation of alkenes via I2 catalysis. Chem Commun 51:10276–10279
Sun X, Li X, Song S, Zhu Y, Liang YF, Jiao N (2015) Mn-catalyzed highly efficient aerobic oxidative hydroxyazidation of olefins: A direct approach to β-azido alcohols. J Am Chem Soc 137(18):6059–6066
Liu Z, Liu J, Zhang L, Liao P, Song J, Bi X (2014) Silver(I)-catalyzed hydroazidation of ethynyl carbinols: synthesis of 2-azidoallyl alcohols. Angew Chem Int Ed 53(21):5305–5309
Liu Z, Liao P, Bi X (2014) General silver-catalyzed hydroazidation of terminal alkynes by combining TMS-N3 and H2O: synthesis of vinyl azides. Org Lett 16(14):3668–3671
Song W, Kozhushkov SI, Ackermann L (2013) Site-selective catalytic c(sp2)-H bond azidations. Angew Chem Int Ed 52(26):6576–6578
Vita MV, Waser J (2015) Cyclic hypervalent iodine reagents and iron catalysts: the winning team for late-stage C–H azidation. Angew Chem Int Ed 54(18):5290–5292
Huang X, Groves JT (2016) Taming azide radicals for catalytic C–H azidation. ACS Catal 6(2):751–759
Grieβ P (1864) Philos Trans R Soc Lond 13:377
Blanksby SJ, Ellison GB (2003) Bond dissociation energies of organic molecules. Acc Chem Res 36(4):255–263
Kita Y, Tohma H, Inagaki M, Hatanaka K, Yakura T (1991) A novel oxidative azidation of aromatic compounds with hypervalent iodine reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA) and trimethylsilyl azide. Tetrahedron Lett 32(34):4321–4324
Kita Y, Tohma H, Hatanaka K, Takada T, Fujita S, Mitoh S, Sakurai H, Oka S (1994) Hypervalent iodine-induced nucleophilic substitution of para-substituted phenol ethers. generation of cation radicals as reactive intermediates. J Am Chem Soc 116(9):3684–3691
Telvekar VN, Sasane KA (2012) Simple and efficient method for the preparation of aryl azides using sonication. Synth Commun 42(7):1085–1089
Tang C, Jiao N (2012) Copper-catalyzed C–H azidation of anilines under mild conditions. J Am Chem Soc 134(46):18924–18927
Fan Y, Wan W, Ma G, Gao W, Jiang H, Zhu S, Hao J (2014) Room-temperature Cu(II)-catalyzed aromatic C–H azidation for the synthesis of ortho-azido anilines with excellent regioselectivity. Chem Commun 50:5733–5736
Xie F, Qi Z, Li X (2013) Rhodium(III)-catalyzed azidation and nitration of arenes by C–H activation. Angew Chem Int Ed 52(45):11862–11866
Yao B, Liu Y, Zhao L, Wang DX, Wang MX (2014) Designing a Cu(II)–ArCu(II)–ArCu(III)–Cu(I) catalytic cycle: Cu(II)-catalyzed oxidative arene C–H bond azidation with air as an oxidant under ambient conditions. J Org Chem 79(22):11139–11145
Lubriks D, Sokolovs I, Suna E (2012) Indirect C–H azidation of heterocycles via copper-catalyzed regioselective fragmentation of unsymmetrical λ3-iodanes. J Am Chem Soc 134(37):15436–15442
Pragati PK, Kalshetti RG, Reddi RN, Kamble SP, Sudalai A (2016) I2-mediated regioselective C-3 azidation of indoles. Org Biomol Chem 14:3027–3030
Li P, Zhao J, Xia C, Li F (2015) The development of carbene-stabilized N–O radical coupling strategy in metal-free regioselective C–H azidation of quinoline N-oxides. Org Chem Front 2:1313–1317
McMillen DF, Golden DM (1982) Hydrocarbon bond dissociation energies. Annu Rev Phys Chem 33:493–532
Bordwell FG (1988) Equilibrium acidities in dimethyl sulfoxide solution. Acc Chem Res 21(12):456–463
Magnus P, Lacour J (1992) New trialkylsilyl enol ether chemistry. Direct.beta.-azido functionalization of triisopropylsilyl enol ethers. J Am Chem Soc 114(2):767–769
Magnus P, Lacour J, Weber W (1993) Direct N-alkyl azidonation of N,N-dialkylarylamines with the iodosylbenzene/trimethylsilyl azide reagent combination. J Am Chem Soc 115(20):9347–9348
Magnus P, Hulme C, Weber W (1994) alpha.-Azidonation of amides, carbamates, and ureas with the iodosylbenzene/trimethylsilyl azide reagent combination: N-acyliminium ion precursors. J Am Chem Soc 116(10):4501–4502
Magnus P, Lacour J, Evans PA, Roe MB, Hulme C (1996) Hypervalent iodine chemistry: new oxidation reactions using the iodosylbenzene–trimethylsilyl azide reagent combination. direct α-and β-azido functionalization of triisopropylsilyl enol ethers. J Am Chem Soc 118(14):3406–3418
Kita Y, Tohma H, Takada T, Mitoh S, Fujita S, Gyoten M (1994) A novel and direct alkyl azidation of p-alkylanisoles using phenyl iodine(III) bis(trifluoroacetate) (PIFA) and trimethylsilyl azide. Synlett 6:427–428
Viuf C, Bols M (2001) Radical azidonation of benzylic positions with iodonium azide. Angew Chem Int Ed 40(3):623–625
Pedersen CM, Marinescu LG, Bols M (2005) Radical substitution with azide: TMSN3–PhI(OAc)2 as a substitute of IN3. Org Biomol Chem 3:816–822
Zhdankin VV, Krasutsky AP, Kuehl CJ, Simonsen AJ, Woodward JK, Mismash B, Bolz JT (1996) Preparation, X-ray crystal structure, and chemistry of stable azidoiodinanes derivatives of benziodoxole. J Am Chem Soc 118(22):5192–5197
Sharma A, Hartwig JF (2015) Metal-catalysed azidation of tertiary C–H bonds suitable for late-stage functionalization. Nature 517:600–604
Huang X, Bergsten TM, Groves JT (2015) Manganese-catalyzed late-stage aliphatic C–H azidation. J Am Chem Soc 137(16):5300–5303
Wang Y, Li GX, Yang G, He G, Chen G (2016) A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C–H bonds. Chem Sci 7:2679–2683
Rabet PT, Fumagalli G, Boyd S, Greaney MF (2016) Benzylic C–H azidation using the ahdankin reagent and a copper photoredox catalyst. Org Lett 18(7):1646–1649
Zhang X, Yang H, Tang P (2015) Transition-metal-free oxidative aliphatic C–H azidation. Org Lett 17(23):5828–5831
Harschneck T, Hummel S, Kirsch SF, Klahn P (2012) Practical azidation of 1,3-dicarbonyls. Chem Eur J 18(4):1187–1193
Galligan MJ, Akula R, Ibrahim H (2014) Unified strategy for iodine(III)-mediated halogenation and azidation of 1,3-dicarbonyl compounds. Org Lett 16(2):600–603
Vita MV, Waser J (2013) Azidation of β-keto esters and silyl enol ethers with a benziodoxole reagent. Org Lett 15(13):3246–3249
Deng QH, Bleith T, Wadepohl H, Gade LH (2013) Enantioselective iron-catalyzed azidation of β-keto esters and oxindoles. J Am Chem Soc 135(14):5356–5359
Lee JG, Kwak KH (1992) Oxidation of aldehydes to acyl azides by chromic anhydride-azidotrimethylsilane. Tetrahedron Lett 33(22):3165–3166
Elmorsy SS (1995) Oxidation of aldehydes to acyl azides using triazidochlorosilane (TACS)-active manganese dioxide reagent. Tetrahedron Lett 36(8):1341–1342
Chen DJ, Chen ZC (2000) Hypervalent iodine in synthesis. Part 54: one-step conversion of aryl aldehydes to aroyl azides using a combined reagent of (diacetoxyiodo)benzene with sodium azide. Tetrahedron Lett 41(38):7361–7363
Bose DS, Reddy AVN (2003) Iodine(V) reagents in organic synthesis. Dess–Martin periodinane mediated efficient one-pot oxidation of aldehydes to acyl azides. Tetrahedron Lett 44(17):3543–3545
Arote ND, Akamanchi KG (2007) Direct conversion of aldehydes to acyl azides using tert-butyl hypochlorite. Tetrahedron Lett 48(32):5661–5664
Marinescu L, Thinggaard J, Thomsen IB, Bols M (2003) Radical azidonation of aldehydes. J Org Chem 68(24):9453–9455
Sarkar SD, Studer A (2010) Oxidative amidation and azidation of aldehydes by NHC catalysis. Org Lett 12(9):1992–1995
Shinomoto Y, Yoshimura A, Shimizu H, Yamazaki M, Zhdankin VV, Saito A (2015) Tetra-n-butylammonium iodide catalyzed C–H azidation of aldehydes with thermally stable azidobenziodoxolon. Org Lett 17(21):5212–5215
Emmett MR, Grover HK, Kerr MA (2012) Tandem ring-opening decarboxylation of cyclopropane hemimalonates with sodium azide: a short route to γ-aminobutyric acid esters. J Org Chem 77(15):6634–6637
Haveli SD, Roy S, Vibha G, Parmar KC, Chandrasekaran S (2013) Ring opening of activated cyclopropanes with NIS/NaN3: synthesis of C-1 linked pseudodisaccharides. Tetrahedron 69(52):11138–11143
Kishore G, Gautam V, Chandrasekaran S (2014) Novel synthesis of carbohydrate fused α-amino γ-lactams and glycopeptides by NIS mediated ring opening of donor–acceptor substituted cyclopropanes. Carbohyd Res 390:1–8
Ivanov KL, Villemson EV, Budynina EM, Ivanova OA, Trushkov IV, Melnikov MY (2015) Ring opening of donor-acceptor cyclopropanes with the azide ion: a tool for construction of N-heterocycles. Chem Eur J 21(13):4975–4987
Gibson DH, DePuy CH (1974) Cyclopropanol chemistry. Chem Rev 74(6):605–623
Kulinkovich OG (2003) The chemistry of cyclopropanols. Chem Rev 103(7):2597–2632
Jiao J, Nguyen LX, Patterson DR, Flowers RA II (2007) An efficient and general approach to β-functionalized ketones. Org Lett 9(7):1323–1326
Ren R, Zhao H, Huan L, Zhu C (2015) Manganese-catalyzed oxidative azidation of cyclobutanols: regiospecific synthesis of alkyl azides by C–C bond cleavage. Angew Chem Int Ed 127(43):12883–12887
Masterson DS, Porter NA (2002) Diastereoselective free radical halogenation, azidation, and rearrangement of β-silyl barton esters. Org Lett 4(24):4253–4256
Nyfeler E, Renaud P (2008) Decarboxylative radical azidation using MPDOC and MMDOC esters. Org Lett 10(5):985–988
Klahn P, Erhardt H, Kotthaus A, Kirsch SF (2014) The synthesis of α-azidoesters and geminal triazides. Angew Chem Int Ed 53(30):7913–7917
Liu C, Wang X, Li Z, Cui L, Li C (2015) Silver-catalyzed decarboxylative radical azidation of aliphatic carboxylic acids in aqueous solution. J Am Chem Soc 137(31):9820–9823
Zhu Y, Li X, Wang X, Huang X, Shen T, Zhang Y, Sun X, Zou M, Song S, Jiao N (2015) Silver-catalyzed decarboxylative azidation of aliphatic carboxylic acids. Org Lett 17(19):4702–4705
Feng P, Sun X, Su Y, Li X, Zhang LH, Shi X, Jiao N (2014) Ceric ammonium nitrate (CAN) catalyzed modification of ketones via two C–C bond cleavages with the retention of the oxo-group. Org Lett 16(12):3388–3391
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2017 Springer Nature Singapore Pte Ltd.
About this chapter
Cite this chapter
Zhang, B., Jiao, N. (2017). Nitrogenation Strategy for the Synthesis of Organic Azides. In: Jiao, N. (eds) Nitrogenation Strategy for the Synthesis of N-containing Compounds. Springer, Singapore. https://doi.org/10.1007/978-981-10-2813-7_6
Download citation
DOI: https://doi.org/10.1007/978-981-10-2813-7_6
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-10-2811-3
Online ISBN: 978-981-10-2813-7
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)