Imidazole-1-sulfonyl Azide Hydrochloride

Introduction

Imidazole-1-sulfonyl azide hydrochloride (1) is a white, slightly hygroscopic solid (mp 100–102 °C) that is soluble in water, acetonitrile, DMSO, DMF, and lower alcohols. It was reported by Goddard-Borger and Stick as a crystalline, shelf-stable, and easily prepared alternative to triflyl azide (TfN₃) in diazotransfer reactions.[1] It is widely used to prepare organic azides from aminosugars, aminoacids, and anilines because of its solubility in water. In addition, this reagent allows conversion of substrates with activated methylene groups into diazo compounds.[1] [2]

The preparation of imidazole-1-sulfonyl azide is conducted by a convenient two-step procedure (Scheme [1]).[1] First, sulfuryl chloride is reacted with NaN₃ to give ClSO₂N₃, which then reacts with imidazole. The crude base product is precipitated by ethanolic HCl.

Scheme 1 Goddard-Borger’s synthesis

To minimize explosion risks, a safer synthesis starting from sulfuryl diimidazole was developed (Scheme [2]).[3]

Scheme 2 Wang’s synthesis

• References

• 1a Goddard-Borger ED, Stick RV. Org. Lett. 2007; 9: 3797
• 1b Goddard-Borger ED, Stick RV. Org. Lett. 2011; 13: 2514
• 2 Maas G. Angew. Chem. Int. Ed. 2009; 48: 8186
• 3 Ye H, Liu R, Li D, Liu Y, Yuan H, Guo W, Zhou L, Cao X, Tian H, Shen J, Wang PG. Org. Lett. 2013; 15: 18
• 4 Smith NM, Greaves MJ, Jewell R, Perry MW. D, Stocks MJ, Stonehouse JP. Synlett 2009; 1391
• 5 Bastian AA, Warszawik EM, Panduru P, Arenz C, Herrmann A. Chem. Eur. J. 2013; 19: 9151
• 6a van Dongen SF. M, Teeuwen RL. M, Nallani M, van Berkel SS, Cornelissen JJ. L. M, Nolte RJ. M, van Hest JC. M. Bioconjugate Chem. 2009; 20: 20
• 6b van Dongen SF. M, Nallani M, Cornelissen JJ. L. M, Nolte RJ. M, van Hest JC. M. Chem. Eur. J. 2009; 15: 1107
• 6c Lipinski T, Luu T, Kitov PI, Szpacenko A, Bundle DR. Glycoconj. J. 2011; 28: 149
• 6d Broyer RM, Schopf E, Kolodziej CM, Chen Y, Maynard HD. Soft Matter 2011; 9972
• 6e Ran Q, Peng R, Liang C, Ye S, Xian Y, Zhang W, Jin L. Talanta 2011; 83: 1381
• 7 Schoffelen S, van Eldijk MB, Rooijakkers B, Raijmakers R, Heck AJ. R, van Hest JC. M. Chem. Sci. 2011; 2: 701
• 8 Hansen MB, van Gurp TH. M, van Hest JC. M, Löwik DW. P. M. Org. Lett. 2012; 14: 2330
• 9 Delville MM. E, Nieuwland PJ, Janssen P, Koch K, van Hest JC. M, Rutjes FP. J. T. Chem. Eng. J. 2011; 167: 556
• 10 Kulbokaite R, Ciuta G, Netopilik M, Makuska R. React. Funct. Polym. 2009; 69: 771
• 11a Tosh DK, Yoo LS, Chinn M, Hong K, Kilbey II SM, Barrett MO, Fricks IP, Harden TK, Gao Z.-G, Jacobson KA. Bioconjugate Chem. 2010; 21: 372
• 11b Kecskés A, Tosh DK, Wei Q, Gao Z.-G, Jacobson KA. Bioconjugate Chem. 2011; 22: 1115
• 12 Verch A, Hahn H, Krause E, Cölfen H, Börner HG. Chem. Commun. 2010; 8938
• 13 Guiard J, Fiege B, Kitov PI, Peters T, Bundle DR. Chem. Eur. J. 2011; 17, 7438
• 14 Castro V, Blanco-Canosa J.-B, Rodriguez H, Albericio F. ACS Comb. Sci. 2013; 15: 331
• 15 McCarthy SA, Davies G.-L, Gunko YK. Nat. Protoc. 2012; 7: 1677
• 16a Lartia R, Murat P, Dumy P, Defrancq E. Org. Lett. 2011; 13: 5672
• 16b Lartia R, Bonnat L, Murat P, Defrancq E. Curr. Protoc. Nucleic Acid Chem. 2012; 50: 4.50:4.50.1-4.50.7