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Synthesis of alkyl azides

Recent Literature

A practical, rapid, and efficient microwave (MW) promoted nucleophilic substitution of alkyl halides or tosylates with alkali azides, thiocyanates or sulfinates in aqueous media tolerates various reactive functional groups.
Y. Ju, D. Kumar, R. S. Varma, J. Org. Chem., 2006, 71, 6697-6700.

Secondary and tertiary alkyl iodides and dithiocarbonates are easily converted into the corresponding azides, either by reaction with ethanesulfonyl azide in the presence of dilauroyl peroxide, or by treatment with benzenesulfonyl azide and hexabutylditin in the presence of a radical initiator.
C. Ollivier, P. Renaud, J. Am. Chem. Soc., 2001, 123, 4717-4727.

Azide transfer of 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP) to alcohols proceeds to give the corresponding azides under mild reaction conditions. The organic azides were easily isolated because the byproducts are highly soluble in water.
M. Kitamura, T. Koga, M. Yano, T. Okauchi, Synlett, 2012, 23, 1335-1338.

Bis(2,4-dichlorophenyl) phosphate mediates an efficient one-pot preparation of alkyl azides from alkanols in the presence of 4-(dimethylamino)pyridine as a base. Phosphorylpyridinium azide is believed to be the activating agent under these conditions.
C. Yu, B. Liu, L. Hu, Org. Lett., 2000, 2, 1959-1961.

A cocatalytic effect of nitro compounds enables a B(C₆F₅)₃·H₂O catalyzed azidation of tertiary aliphatic alcohols with a broad range of substrates. Kinetic, electronic, and spectroscopic evidence suggests that higher order hydrogen-bonded aggregates of nitro compounds and acids are the kinetically competent Brønsted acid catalysts.
M. Dryzhakov, M. Hellal, E. Wolf, F. C. Falk, J. Moran, J. Am. Chem. Soc., 2015, 137, 9555-9558.

Unactivated olefins are converted to alkyl azides with bench-stable NaN₃ in the presence of FeCl₃·6H₂O under blue-light irradiation. The products are obtained with anti-Markovnikov selectivity, and the reaction can be performed under mild ambient conditions in the presence of air and moisture. The transformation displays broad functional group tolerance.
H. Lindner, W. M. Amberg, E. M. Carreira, J. Am. Chem. Soc., 2023, 145, 22347-22353.

A direct intermolecular anti-Markovnikov hydroazidation method for unactivated olefins is promoted by a catalytic amount of bench-stable benziodoxole at ambient temperature. This method facilitates previously difficult, direct addition of hydrazoic acid across a wide variety of unactivated olefins.
H. Li, S.-J. Shen, C.-L. Zhu, H. Xu, J. Am. Chem. Soc., 2019, 141, 9415-9421.

With AgNO₃ as the catalyst and K₂S₂O₈ as the oxidant, an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous MeCN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed.
C. Liu, X. Wang, Z. Li, L. Cui, C. Li, J. Am. Chem. Soc., 2015, 137, 9820-9823.

In a catalytic decarboxylative nitrogenation, a series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K₂S₂O₈ as the oxidant and PhSO₂N₃ as the nitrogen source via an alkyl radical process.
Y. Zhu, X. Liu, X. Wang, X. Huang, T. Shen, Y. Zhang, X. Sun, M. Zou, S. Song, N. Jiao, Org. Lett., 2015, 17, 4702-4705.

A cobalt-catalyzed hydroazidation of α,α-disubstituted olefins with commercially available azide sources provides tertiary azides in useful yields and tolerates a variety of functional groups.
B. Gaspar, J. Waser, E. M. Carreira, Synthesis, 2007, 3839-3845.

A highly Marknovikov selectiv conversion of various olefins to azides was achieved using a cobalt catalyst, 3 equiv of TsN₃ as nitrogen source and simple silanes (PhSiH₃, TMDSO).
J. Waser, H. Nambu, E. M. Carreira, J. Am. Chem. Soc., 2005, 127, 8294-8295.

An organic acridinium salt catalyzes an anti-Markovnikov hydroazidation of activated olefins under irradiation from blue LEDs. This method is applicable to a variety of substituted styrenes and several vinyl ethers, yielding synthetically versatile hydroazidation products in excellent yield, whereas terminal styrenes provide hydroazidation products in moderate yields.
N. P. R. Onuska, M. E. Schutzbach-Horton, J. L. R. Collazo, D. A. Nicewicz, Synlett, 2020, 31, 55-59.

The combination of sodium periodate, potassium iodide, and sodium azide is an efficient, simple, and inexpensive reagent system for azidoiodination of alkenes. The regiospecific 1,2-azidoiodination proceeds in an anti-Markovnikov fashion to produce β-iodoazides in excellent yields.
P. V. Chouthaiwale, P. U. Karabal, G. Suryavanshi, A. Sudalai, Synthesis, 2010, 3879-3882.

An operationally simple iron-catalyzed difunctionalization of alkenes provides primary 2-azidoamines, which are versatile precursors to vicinal diamines. A wide array of alkene substrates are tolerated, including complex drug-like molecules and a tripeptide. Facile, chemoselective derivatizations of the azidoamine group demonstrate the versatility of this masked diamine motif.
S. Makai, E. Falk, B. Morandi, J. Am. Chem. Soc., 2020, 142, 21548-21555.

A general, catalytic, and enantioselective synthesis of α-amino acids
E. J. Corey, J. O. Link, J. Am. Chem. Soc., 1992, 114, 1906-1908.

A photoredox-catalyzed azidotrifluoromethylation of substituted styrenes as well as various activated and nonactivated alkenes using [Ru(bpy)₃(PF₆)₂] as the photocatalyst and Umemoto’s reagent as the CF₃ source delivers a wide range β-trifluoromethylated azides or amines in good yields.
G. Dagousset, A. Carboni, E. Magnier, G. Masson, Org. Lett., 2014, 16, 4340-4343.