Synlett 2012; 23(10): 1554-1555
DOI: 10.1055/s-0031-1290687
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© Georg Thieme Verlag Stuttgart · New York

Azidotrimethylsilane

Bao-Le Li
The College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050024, P. R. of China, eMail: lible_111@163.com
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Publikationsverlauf

Publikationsdatum:
29. Mai 2012 (online)

 
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Bao-Le Li was born in Hengshui, Hebei Province (P. R. of China) in 1987. He graduated from the Hebei Normal University and received his B.Sc. in chemistry in 2011. Currently, he is working towards his M.Sc. degree under the supervision of Professor Zhan-Hui Zhang at the same university. His current interests are the development of new methods for the synthesis of biologically active heterocyclic compounds.

Introduction

Azidotrimethylsilane (TMSN3) is a clear, colorless, quite stable organosilane reagent and decomposes slowly even at 200 °C. It is considered a very convenient and safer replacement for hydrazoic acid as an azide source in many reactions.[ 1 ] It has been used for the synthesis of aryl 1,2,3-triazoles,[2] [3] [4] [5] tetrazoles,[ 6,7 ] functionalized bicyclic triazoles,[ 8 ] azides,[9] [10] [11] [12] [13] [14] [15] and N-tetrazolated diamine derivative.[ 16 ] In addition, azidotrimethylsilane has been employed for the preparation of proline-derived chiral aminotriazole ligands.[ 17 ] It was found to be a useful reagent for the aziridine ring opening to obtain azidomethyl-substituted pyrrole precursors,[ 18 ] or kinetic resolution of monosubstituted epoxide for the synthesis of optically pure 1-azido-2-trimethylsiloxyalkanes.[ 19 ]

Azidotrimethylsilane can be conveniently and rapidly prepared by adding chlorotrimethylsilane dropwise to a stirred solution of NaN3 in diethylene glycol dimethyl ether.[ 1 ]

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Scheme 1

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Abstracts

(A) One-Pot Rearrangement of Carboxylic Acids to Carbamates:

Augustine and co-workers have developed a simple and efficient procedure for a one-pot conversion of carboxylic acids into carbamates through the Curtius rearrangement by employing propylphosphonic anhydride (T3P®) and azidotrimethylsilane in the presence of an alcohol.[ 20 ]

(B) Preparation of α-Azido Oximes:

Sukhorokov and co-workers reported that α-azido oximes could be obtained from aliphatic nitro compounds via interaction of N,N-bis(silyloxy)enamines with trimethylsilylazide.[ 21 ]

(C) Synthesis of Chiral Terminal 1,2-Diamines:

A regioselective ring opening of aziridines with TMSN3 has been developed and the azido group and the double bond were reduced by LiAlH4 to give chiral terminal 1,2-diamines in high yields.[ 22 ]

(D) Synthesis of Fullerenyl Azide:

In the presence of a Lewis acid, the first fullerenyl azide compound has been synthesized via addition of azidotrimethylsilane effectively to a cage-opened fullerene derivative.[ 23 ]

(E) Synthesis of Tetrazoles:

Direct conversion of 1,3-diarylprop-1-enes into tetrazole was demonstrated in the presence of azidotrimethylsilane and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) using CuI as the catalyst at 80 °C in MeCN.[ 24 ]

(F) Synthesis of Triazolothiadiazepine-1,1-dioxides:

Recently, a one-pot synthesis of triazolothiadiazepine-1,1-dioxides via copper-catalyzed [3+2] cycloaddition has been achieved in the presence of azidotrimethylsilane and Hünig’s base (DIPEA).[ 25 ]

(G) Azidation of Hemiketals:

Azidotrimethylsilane is also used as an efficient azide source for azidation of hemiketals using molecular iodine as promoter. The reaction proceeded smoothly at room temperature to afford the desired glycosylazide as a single isomer in good yield.[ 26 ]

(H) Oxidative Azidation of Aldehydes:

In addition to the above cases, azidotrimethylsilane can also be applied as an azide source of reaction oxidative azidation of aldehydes in the presence of 1,3-dimethyltriazolium iodide, 1,8-diazabicy­clo[5.4.0]undec-7-ene (DBU) and 3,3,5,5-tetra-tert-butyldiphenoquinone.[ 27 ]


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  • References

  • 1 Birkofer L, Wegner P. Org. Syn. 1970; 50: 107
  • 2 Stazi F, Cancogni D, Turco L, Westerduin P, Bacchi S. Tetrahedron Lett. 2010; 51: 5385
  • 3 Fukuzawa SI, Shimizu E, Kikuchi S. Synlett 2007; 2436
  • 4 Majumdar KC, Ray K. Synthesis 2011; 3767
  • 5 Smith AG, Johnson JS. Org. Lett. 2010; 12: 1809
  • 6 Kennedy LJ. Tetrahedron Lett. 2010; 51: 2010
  • 7 Kumar MR, Park K, Lee S. Adv. Synth. Catal. 2010; 352: 3255
  • 8 Kim MS, Yoon HJ, Lee BK, Kwon JH, Lee WK, Kim Y, Ha HJ. Synlett 2005; 2187
  • 9 Zapico JM, Serra P, García-Sanmartín J, Filipiak K, Carbajo RJ, Schott AK, Pineda-Lucena A, Martínez A, Martín-Santamaría S, Pascual-Teresa B, Ramos A. Org. Biomol. Chem. 2011; 9: 4587
  • 10 Chan LY, Kim S, Chung WT, Long C, Kim S. Synlett 2011; 415
  • 11 Montagu A, Roy V, Balzarini J, Snoeck R, Andrei G, Agrofoglio LA. Eur. J. Med. Chem. 2011; 46: 778
  • 12 Shetti VS, Ravikanth M. Eur. J. Org. Chem. 2010; 494
  • 13 Tsai C.-S, Liu P.-Y, Yen H.-Y, Hsua T.-L, Wong C.-H. Chem. Commun. 2011; 46: 5575
  • 14 Smith AG, Johnson JS. Org. Lett. 2010; 12: 1784
  • 15 Hu HG, Wang SZ, Zhang CM, Wang L, Ding L, Zhang JP, Wu Q. Bioorg. Med. Chem. Lett. 2010; 20: 7537
  • 16 Athanassopoulos CM, Garnelis T, Magoulas G, Papaioannou D. Synthesis 2006; 3134
  • 17 Cambeiro XC, Pericãs MA. Adv. Synth. Catal. 2011; 353: 113
  • 18 Kim JH, Lee SB, Lee WK, Yoon DH, Ha HJ. Tetrahedron 2011; 67: 3553
  • 19 Larrow JF, Schaus SE, Jacobsen EN. J. Am. Chem. Soc. 1996; 118: 7420
  • 20 Augustine JK, Bombrun A, Mandal AB, Alagarsamy P, Atta RN, Selvam P. Synthesis 2011; 1477
  • 21 Sukhorokov AY, Bliznets IV, Lesiv AV, Khomutova YA, Strelenko YA. Synthesis 2005; 1077
  • 22 Lee BK, Kim MS, Hahm HS, Kim DS, Lee WK, Ha HG. Tetrahedron 2006; 62: 8393
  • 23 Jiang ZP, Xiao Z, Zhang GH, Gan LB, Wang D, Zhang WX. Tetrahedron Lett. 2010; 51: 415
  • 24 Chen F, Qin C, Cui YX, Jiao N. Angew. Chem. Int. Ed. 2011; 50: 11487
  • 25 Barange DK, Tu YC, Kavala V, Kuo CW, Yao CF. Adv. Synth. Catal. 2010; 353: 41
  • 26 Pal AP. J, Mallick A, Reddy YS, Vankar YD. Tetrahedron Lett. 2010; 51: 6334
  • 27 Sarkar SD, Studer A. Org. Lett. 2010; 12: 1992

  • References

  • 1 Birkofer L, Wegner P. Org. Syn. 1970; 50: 107
  • 2 Stazi F, Cancogni D, Turco L, Westerduin P, Bacchi S. Tetrahedron Lett. 2010; 51: 5385
  • 3 Fukuzawa SI, Shimizu E, Kikuchi S. Synlett 2007; 2436
  • 4 Majumdar KC, Ray K. Synthesis 2011; 3767
  • 5 Smith AG, Johnson JS. Org. Lett. 2010; 12: 1809
  • 6 Kennedy LJ. Tetrahedron Lett. 2010; 51: 2010
  • 7 Kumar MR, Park K, Lee S. Adv. Synth. Catal. 2010; 352: 3255
  • 8 Kim MS, Yoon HJ, Lee BK, Kwon JH, Lee WK, Kim Y, Ha HJ. Synlett 2005; 2187
  • 9 Zapico JM, Serra P, García-Sanmartín J, Filipiak K, Carbajo RJ, Schott AK, Pineda-Lucena A, Martínez A, Martín-Santamaría S, Pascual-Teresa B, Ramos A. Org. Biomol. Chem. 2011; 9: 4587
  • 10 Chan LY, Kim S, Chung WT, Long C, Kim S. Synlett 2011; 415
  • 11 Montagu A, Roy V, Balzarini J, Snoeck R, Andrei G, Agrofoglio LA. Eur. J. Med. Chem. 2011; 46: 778
  • 12 Shetti VS, Ravikanth M. Eur. J. Org. Chem. 2010; 494
  • 13 Tsai C.-S, Liu P.-Y, Yen H.-Y, Hsua T.-L, Wong C.-H. Chem. Commun. 2011; 46: 5575
  • 14 Smith AG, Johnson JS. Org. Lett. 2010; 12: 1784
  • 15 Hu HG, Wang SZ, Zhang CM, Wang L, Ding L, Zhang JP, Wu Q. Bioorg. Med. Chem. Lett. 2010; 20: 7537
  • 16 Athanassopoulos CM, Garnelis T, Magoulas G, Papaioannou D. Synthesis 2006; 3134
  • 17 Cambeiro XC, Pericãs MA. Adv. Synth. Catal. 2011; 353: 113
  • 18 Kim JH, Lee SB, Lee WK, Yoon DH, Ha HJ. Tetrahedron 2011; 67: 3553
  • 19 Larrow JF, Schaus SE, Jacobsen EN. J. Am. Chem. Soc. 1996; 118: 7420
  • 20 Augustine JK, Bombrun A, Mandal AB, Alagarsamy P, Atta RN, Selvam P. Synthesis 2011; 1477
  • 21 Sukhorokov AY, Bliznets IV, Lesiv AV, Khomutova YA, Strelenko YA. Synthesis 2005; 1077
  • 22 Lee BK, Kim MS, Hahm HS, Kim DS, Lee WK, Ha HG. Tetrahedron 2006; 62: 8393
  • 23 Jiang ZP, Xiao Z, Zhang GH, Gan LB, Wang D, Zhang WX. Tetrahedron Lett. 2010; 51: 415
  • 24 Chen F, Qin C, Cui YX, Jiao N. Angew. Chem. Int. Ed. 2011; 50: 11487
  • 25 Barange DK, Tu YC, Kavala V, Kuo CW, Yao CF. Adv. Synth. Catal. 2010; 353: 41
  • 26 Pal AP. J, Mallick A, Reddy YS, Vankar YD. Tetrahedron Lett. 2010; 51: 6334
  • 27 Sarkar SD, Studer A. Org. Lett. 2010; 12: 1992

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Scheme 1