Synlett 2015; 26(02): 205-208
DOI: 10.1055/s-0034-1378933
letter
© Georg Thieme Verlag Stuttgart · New York

Reactions of 2-[Lithio(trimethylsilyl)methyl]-2H-tetrazoles: Synthesis of 2-[1-(Trimethylsilyl)alkyl]-2H-tetrazoles and (2H-Tetrazol-2-yl)acetates

Hideaki Umemoto*
a   Fujimoto Chemicals Co., Ltd., 1-2-38 Kinrakuji-cho, Amagasaki 660-0806, Japan   Fax: +81(6)64823115   eMail: h-umemoto@fujimoto-chem.co.jp
,
Takuya Onaka
a   Fujimoto Chemicals Co., Ltd., 1-2-38 Kinrakuji-cho, Amagasaki 660-0806, Japan   Fax: +81(6)64823115   eMail: h-umemoto@fujimoto-chem.co.jp
,
Yasuyoshi Miki
b   School of Pharmaceutical Sciences, Kinki University, 3-4-1 Kowakae, Higashi-Osaka 577-8502, Japan   Fax: +81(6)67212505   eMail: maegawa@phar.kindai.ac.jp
,
Akira Nakamura
b   School of Pharmaceutical Sciences, Kinki University, 3-4-1 Kowakae, Higashi-Osaka 577-8502, Japan   Fax: +81(6)67212505   eMail: maegawa@phar.kindai.ac.jp
,
Tomohiro Maegawa*
b   School of Pharmaceutical Sciences, Kinki University, 3-4-1 Kowakae, Higashi-Osaka 577-8502, Japan   Fax: +81(6)67212505   eMail: maegawa@phar.kindai.ac.jp
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Publikationsverlauf

Received: 07. September 2014

Accepted after revision: 16. Oktober 2014

Publikationsdatum:
27. November 2014 (online)


Abstract

The reaction of 2-[(trimethylsilyl)methyl]-2H-tetrazoles with various alkyl halides and carbonates using n-butyllithium or lithium diisopropylamide (LDA) gave 2-[1-(trimethylsilyl)alkyl]-2H-tetrazoles and (2H-tetrazol-2-yl)acetates as useful synthons of modified tetrazoles.

Supporting Information

 
  • References and Notes

    • 1a Butler RN In Comprehensive Heterocyclic Chemistry . Vol. 4. Katritzky AR, Rees CW, Scriven EF. V. Pergammon; Oxford: 1996
    • 1b Koldobskii GI, Kharbash RB. Russ. J. Org. Chem. 2003; 39: 453
    • 1c Roh J, Vávrová K, Hrabálek A. Eur. J. Org. Chem. 2012; 6101
    • 2a Herr RJ. Bioorg. Med. Chem. 2002; 10: 3379
    • 2b Aureggi V, Sedelmeier G. Angew. Chem. Int. Ed. 2007; 46: 8440
    • 2c Alonen A, Finel M, Kostiainen R. Biochem. Pharmacol. 2008; 76: 763
    • 2d Alonen A, Jansson J, Kallonen S, Kiriazis A, Aitio O, Finel M, Kostiainen R. Bioorg. Chem. 2008; 36: 148
    • 3a Bavetsias V, Jackman AL, Kimbell R, Boyle FT, Bisset GM. F. Bioorg. Med. Chem. Lett. 1996; 6: 631
    • 3b Tamura Y, Watanabe F, Nakatani T, Yasui K, Fuji M, Komurasaki T, Tsuzuki H, Maekawa R, Yoshioka T, Kawada K, Sugita K, Ohtani M. J. Med. Chem. 1998; 41: 640
    • 4a May BC. H, Abell AD. J. Chem. Soc., Perkin Trans. 1 2002; 172
    • 4b Gagnon A, Landry S, Coulombe R, Guse I, Thavonekham B, Bonneau PR, Yoakim C, Simoneau B. Bioorg. Med. Chem. Lett. 2009; 19: 1199
    • 5a Sun Y, Liu D, Or YS, Wang Z. WO 2008 019 289, 2008 ; Chem. Abstr. 2008, 148, 262901
    • 5b Sun Y, Liu D, Or YS, Wang Z. WO 2008 021 733, 2008 ; Chem. Abstr. 2008, 148, 308635
    • 5c Sun Y, Liu D, Or YS, Wang Z. WO 2009 064 955, 2009 ; Chem. Abstr. 2009, 150, 555797.
    • 6a Tehrani LR, Smith ND, Huang D, Poon SF, Roppe JR, Seiders TJ, Chapman DF, Chung J, Cramer M, Cosford ND. P. Bioorg. Med. Chem. Lett. 2005; 15: 5061
    • 6b Arora J, Edwards L, Isaac M, Kers A, Staaf K, Slassi A, Stefanac T, Wensbo D, Xin T, Holm B. WO 2005 080 386, 2005 ; Chem. Abstr. 2005, 143, 266955
    • 6c Arzel E, Edwards L, Isaac M, Mcleod DA, Slassi A, Xin T. WO 2009 051 556, 2009 ; Chem. Abstr. 2009, 150, 447953
  • 7 Lachance N, Li CS, Leclerc J.-P, Ramtohul YK. WO 2008 128 335, 2008 ; Chem. Abstr. 2008, 149, 513832
  • 8 Wood HB, Szewczyk JW, Huang Y, Adams AD. WO 2009 129 036, 2009 ; Chem. Abstr. 2008, 151, 491142
  • 9 Ichikawa M, Ohtsuka M, Ohki H, Haginoya N, Itoh M, Sugita K, Usui H, Suzuki M, Terayama K, Kanda A. Bioorg. Med. Chem. 2012; 20: 3072
    • 10a Chul LS, Yong UM, Ryune CN, Won LD, Young LJ, Ho KH, Ho LD. US Patent 8 501 436, 2010 ; Chem. Abstr. 2010, 154, 86383
    • 10b Rostom SA. F, Ashour HM. A, Razik HA. A. E, Fattah AE. F. H. A. E, El-Din NN. Bioorg. Med. Chem. 2009; 17: 2410
  • 11 Onaka T, Umemoto H, Miki Y, Nakamura A, Maegawa T. J. Org. Chem. 2014; 79: 6703
    • 12a Thomas EW, Cudahy MM. J. Org. Chem. 1993; 58: 1623
    • 12b Moody CJ, Rees CW, Young RG. J. Chem. Soc., Perkin Trans. 1 1991; 323
    • 12c Moody CJ, Rees CW, Young RG. Synlett 1990; 413
  • 13 Zhang S, Zhang X.-M, Bordwell FG. J. Am. Chem. Soc. 1995; 117: 602
  • 14 Einberg F. J. Org. Chem. 1970; 35: 3978
  • 15 Krylov AS, Dogadina AV, Trifonov RE. Russ. J. Org. Chem. 2014; 50: 892
  • 16 Reaction of 2-[2-(Trimethylsilyl)alkyl]-2H-tetrazoles with Alkyl Halides; Typical Procedure for 5-Phenyl-2-[1-(trimethylsilyl)ethyl]-2H-tetrazole (2a):A solution of 1 (0.50 mmol) in anhydrous THF (1 mL) was cooled to –78 °C under an argon atmosphere. n-BuLi (1.6 M in n-hexane, 0.55 mmol) was added to the suspension dropwise over 30 min, and the mixture was stirred further for 1 h. Iodomethane (0.55 mmol) was added to the mixture, which was stirred at –78 °C for 2 h. After quenching with HCl, the reaction mixture was extracted with EtOAc. The organic layer was washed with H2O, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to afford 2a (90%) as a colorless oil.1H NMR (CDCl3): δ = 0.15 [s, 9 H, (CH3)3Si], 1.71 (d, J = 7.6 Hz, 3 H, CH3), 4.52 (q, J = 5.6 Hz, 1 H, CH), 7.42–7.53 (m, 3 H, ArH), 8.12–8.20 (m, 2 H, ArH); 13C NMR (CDCl3): δ = –3.50, 16.23, 51.86, 126.73, 127.90, 128.82, 130.00, 164.49; HRMS (ESI): m/z [M + H]+ calcd for C12H19N4Si: 247.1379; found: 247.1353.
  • 17 Preparation of Acetates and Ketones; Typical Procedure for Methyl (5-Phenyl-2H-tetrazol-2-yl)acetate (3b): A mixture of 1 (0.50 mmol) and dimethyl carbonate (0.55 mmol) in anhydrous THF (1 mL) was cooled to –78 °C under an argon atmosphere. LDA (1.1 M in n-hexane–THF, 1.05 mmol) was added to the suspension dropwise over 60 min. After stirring for 2 h at –78 °C, HCl (1.0 M, 3 mL) was added to the mixture. The mixture was allowed to reach r.t., and stirred for 30 min. The reaction mixture was extracted with EtOAc and the organic layer was washed with H2O, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to afford 3b (88%) as a white solid.Mp 97–98 °C (n-hexane–CHCl3) (Lit.14 93–94 °C); IR (ATR): 1756 cm–1; 1H NMR (CDCl3): δ = 3.83 (s, 3 H, COOCH3), 5.48 (s, 2 H, CH2), 7.47–7.53 (m, 3 H, ArH), 8.13–8.20 (m, 2 H, ArH); 13C NMR (CDCl3): δ = 53.23, 53.31, 127.01, 127.04, 128.93, 130.56, 165.53, 165.71; HRMS (ESI): m/z [M + H]+ calcd for C10H11N4O2: 219.0882; found: 219.0872.
  • 18 Multicomponent Reaction of 2-[1-(Trimethylsilyl)methyl]-2H-tetrazole; Typical Procedure for Dimethyl 2-(5-Phenyl-2H-tetrazol-2-yl)malonate (4a): A mixture of 1 (0.50 mmol) and dimethyl carbonate (0.55 mmol) in anhydrous THF (1 mL) was cooled to –78 °C under an argon atmosphere. LDA (1.1 M in n-hexane–THF, 1.05 mmol) was added to the suspension dropwise over 30 min. After stirring for 30 min, methyl chloroformate (1.05 mmol) was added to the mixture. The mixture allowed to reach 10 °C slowly, and stirred overnight. After quenching with HCl, the reaction mixture was extracted with EtOAc and the organic layer was washed with H2O, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to afford 4a (51%) as a colorless oil.IR (ATR): 1752 cm–1; 1H NMR (CDCl3): δ = 3.91 (s, 6 H, COOCH3), 6.37 (s, 1 H, CH), 7.47–7.51 (m, 3 H, ArH), 8.16–8.22 (m, 2 H, ArH); 13C NMR (CDCl3): δ = 54.13, 66.61, 126.73, 127.14, 128.87, 130.70, 162.51, 165.69; HRMS (ESI): m/z [M + H]+ calcd for C12H13N4O2: 277.0937; found: 277.0927.