Synlett 2012(3): 367-370  
DOI: 10.1055/s-0031-1290326
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Novel Photolabile Protecting Group for Phosphate Compounds

Youlai Zhang, Hiroki Tanimoto, Yasuhiro Nishiyama, Tsumoru Morimoto, Kiyomi Kakiuchi*
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0101, Japan
Fax: +81(743)726089; e-Mail: kakiuchi@ms.naist.jp;
Further Information

Publication History

Received 25 October 2011
Publication Date:
27 January 2012 (eFirst)

Abstract

A novel photolabile protecting group, thiochromone S,S-dioxide, containing the diazomethyl group for protection of phosphate derivatives is described. Deprotection of the successfully protected phosphate derivatives proceeded smoothly under photoirradiation using an ultrahigh-pressure mercury lamp to recover the corresponding phosphates quantitatively, and the photoproduct derived from the thiochromone derivative showed high fluorescence intensity.

    References and Notes

  • 1a Mayer G. Heckel A. Angew. Chem. Int. Ed.  2006,  45:  4900 
  • 1b Igarashi T. Shimokawa M. Iwasaki M. Nagata K. Fujii M. Sakurai T. Synlett  2007,  1436 
  • 1c Bochet CG. J. Chem. Soc., Perkin Trans. 1  2002,  125 
  • 2a Fodor SPA. Read JL. Pirrung MC. Stryer L. Lu AT. Solas D. Science  1991,  251:  767 
  • 2b Mcgall GH. Barone AD. Diggelmann M. Fodor SPA. Gentalen E. Ngo N. J. Am. Chem. Soc.  1997,  119:  5081 
  • 2c Mayer G. Heckel A. Angew. Chem. Int. Ed.  2006,  45:  4900 
  • 3a Pillai VNR. Org. Photochem.  1987,  9:  225 
  • 3b Givens RS. Kueper LW. Chem. Rev.  1993,  93:  55 
  • 3c Guillier F. Orain D. Bradley M. Chem. Rev.  2000,  100:  2091 
  • 3d Pelliccioli AP. Wirz J. Photochem. Photobiol. Sci.  2002,  1:  441 
  • 3e Mayer G. Heckel A. Angew. Chem. Int. Ed.  2006,  45:  4900 
  • 3f Wang PF. Hu HY. Wang Y. Org. Lett.  2007,  9:  1533 
  • 4 Givens RS. Kueper LW. Chem. Rev.  1993,  93:  55 
  • 5 Kitani S. Sugawara K. Tsutsumi K. Morimoto T. Kakiuchi K. Chem. Commun.  2008,  2103 
  • 6a Ito K. Maruyama J. Chem. Pharm. Bull.  1983,  31:  3014 
  • 6b Ito K. Maruyama J. Chem. Pharm. Bull.  1987,  35:  1255 
  • 7 In this step, we observed an interesting side reaction and for details, see: Zhang Y. Tanimoto H. Nishiyama Y. Morimoto T. Kakiuchi K. Heterocycles  2011,  83:  2337 
8

Analytical and Spectral Data of 6 Yellow solid; mp 213.7-214.2 ˚C. IR (KBr): 1685, 1310 cm. ¹H NMR (500 MHz, CDCl3/TMS): δ = 9.54 (1 H, s), 8.24 (1 H, d, J = 6.7 Hz), 8.15 (1 H, d, J = 7.9 Hz), 7.97 (1 H, dd, J = 7.9, 7.9 Hz), 7.83 (1 H, dd, J = 6.7, 7.9 Hz), 7.63 (1 H, dd, J = 7.3, 7.9 Hz), 7.56 (2 H, dd, J = 7.9, 7.3 Hz), 7.37 (2 H, d, J = 6.7 Hz). ¹³C NMR (125 MHz, CDCl3/TMS): δ = 185.3, 179.5, 148.7, 141.8, 141.2, 135.7, 133.4, 131.5, 131.1, 129.0, 128.7, 128.5, 128.1, 123.4. HRMS (EI): m/z calcd for C16H10O4S [M+]: 298.0300; found: 298.0298.

9

Analytical and Spectral Data of 7 Yellow solid; mp 165.5-167.8 ˚C. IR (KBr): 3420, 2359 cm. ¹H NMR (500 MHz, CDCl3/TMS): δ = 8.20 (3 H, m), 7.92 (1 H, dd, J = 7.9 Hz), 7.81 (2 H, d, J = 8.5 Hz), 7.78 (1 H, dd, J = 7.9 Hz), 7.50 (3 H, m), 7.32 (2 H, d, J = 8.5 Hz), 7.19 (2 H, d, J = 7.0 Hz), 5.30 (1 H, s), 2.42 (3 H, s). ¹³C NMR (125 MHz, CDCl3/TMS): δ = 178.1, 145.0, 144.3, 143.4, 142.2, 142.1, 136.8, 135.0, 134.5, 133.0, 130.8, 129.9, 129.8, 128.6, 128.6, 128.3, 128.2, 123.4, 21.7. HRMS-FAB: m/z calcd for C23H1 8N2O5S2 [M + H]+: 467.0735; found: 467.0742.

10

Analytical and Spectral Data of 1b
Yellow solid; mp 122.3-123.5 ˚C. IR (KBr): 3433, 2359 cm. ¹H NMR (500 MHz, CDCl3/TMS): δ = 8.26 (1 H, d, J = 7.9 Hz), 8.06 (1 H, d, J = 7.9 Hz), 7.85 (1 H, dd, J = 7.9 Hz), 7.79 (1 H, dd, J = 7.9 Hz), 7.48 (3 H, m), 7.27 (2 H, d, J = 7 Hz), 4.95 (1 H, s). ¹³C NMR (125 MHz, CDCl3/TMS): δ = 175.0, 139.6, 133.5, 133.5, 132.5, 129.8, 129.6, 129.1, 128.9, 128.8, 128.7, 127.4, 122.7, 47.5. HRMS-ESI: m/z calcd for C32H20O6S2Na [2 M - 2 N2 + Na]+: 587.0599; found: 587.0600.

11

Treatment of 8h with 2.5 equiv of 1b in the presence of a catalytic amount of 10% HCl aq in CHCl3 at 60 ˚C afforded diprotection product in 81% yield. The complete experi-mental procedures and analytical data are shown in the Supporting Information.