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Volume 69 
Part 7 
Pages o1069-o1070  
July 2013  

Received 9 May 2013
Accepted 5 June 2013
Online 12 June 2013

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.003 Å
R = 0.044
wR = 0.127
Data-to-parameter ratio = 15.9
Details
Open access

1-O-Benzyl-2,3-O-isopropylidene-6-O-tosyl-[alpha]-L-sorbofuranose

aSchool of Chemistry (F11), University of Sydney, NSW 2006, Australia,bCrystal Structure Analysis Facility, School of Chemistry (F11), University of Sydney, NSW 2006, Australia,cDepartment of Hospital Pharmacy, University of Toyama, 2630, Sugitani, Toyama 930-0194, Japan, and dInstitute for Glycomics, Gold Coast Campus, Griffith University, Queensland 4222, Australia
Correspondence e-mail: simone_m@chem.usyd.edu.au

In the title compound (systematic name: {(3aS,5S,6R,6aS)-3a-[(benzyloxy)methyl]-6-hydroxy-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl}methyl 4-methylbenzenesulfonate), C23H28O8S, the absolute structure and relative stereochemistry of the four chiral centres have been established by X-ray crystallography, with the absolute configuration inferred from the use of L-sorbose as the starting material. The central furanose ring adopts a slightly twisted envelope conformation (with the C atom bearing the methylbenzenesulfonate substituent as the flap) from which three substituents depart pseudo-axially (-CH2-O-benzyl, -OH and one acetonide O atom) and two substituents pseudo-equatorially (-CH2-O-tosyl and second acetonide O atom). The dioxalane ring is in a flattened envelope conformation with the fused CH C atom as the flap. In the crystal, molecules pack in columns along [010] linked by O-H...O hydrogen bonds involving the furanose hydroxy group and furanose ether O atom.

Related literature

The title compound is a novel intermediate in the synthesis of 1-deoxynojirimycin (DNJ) analogues. For examples of the use of monosaccharide starting materials in iminosugar syntheses, see: Compain & Martin (2001[Compain, P. & Martin, O. R. (2001). Bioorg. Med. Chem. 9, 3077-3092.]); Cipolla et al. (2003[Cipolla, L., La Ferla, B. & Nicotra, F. (2003). Curr. Top. Med. Chem. 3, 485-511.]); Best, Wang et al. (2010[Best, D., Wang, C., Weymouth-Wilson, A. C., Clarkson, R. A., Wilson, F. X., Nash, R. J., Miyauchi, S., Kato, A. & Fleet, G. W. J. (2010). Tetrahedron Asymmetry, 21, 311-319.]); Wilkinson et al. (2010[Wilkinson, B. L., Bornaghi, L. F., Lopez, M., Poulsen, S.-A., Healy, P. C. & Houston, T. A. (2010). Aust. J. Chem. 63, 821-829.]); Nash et al. (2011[Nash, R. J., Kato, A., Yu, C.-Y. & Fleet, G. W. J. (2011). Fut. Med. Chem. 3, 1513-1521.]); Zhang et al. (2011[Zhang, Z.-X., Wu, B., Wang, B., Li, T.-H., Zhang, P.-F., Guo, L.-N., Wang, W.-J., Zhao, W. & Wang, P. G. (2011). Tetrahedron Lett. 52, 3802-3805.]); Lenagh-Snow et al. (2011[Lenagh-Snow, G. M. J., Araujo, N., Jenkinson, S. F., Rutherforf, C., Nakagawa, S., Kato, A., Yu, C.-Y., Weymouth-Wilson, A. C. & Fleet, G. W. J. (2011). Org. Lett. 13, 5834-5837.]); Simone et al. (2012[Simone, M. I., Soengas, R. G., Jenkinson, S. F., Evinson, E. L., Nash, R. J. & Fleet, G. W. J. (2012). Tetrahedron Asymmetry, 23, 401-408.]); Soengas et al. (2012[Soengas, R. G., Simone, M., Hunter, S., Nash, R. J. & Fleet, G. W. J. (2012). Eur. J. Org. Chem. 12, 2394-2402.]); Kato et al. (2012[Kato, A., Hayashi, E., Miyauchi, S., Adachi, I., Imahori, T., Natori, Y., Yoshimura, Y., Nash, R. J., Shimaoka, H., Nakagome, I., Koseki, J., Hirono, S. & Takahata, H. (2012). J. Med. Chem. 55, 10347-10362.]). For examples of the synthesis of other biologically active compounds from monosaccharides, see: Compain et al. (2009[Compain, P., Chagnault, V. & Martin, O. R. (2009). Tetrahedron Asymmetry, 20, 672-711.]); Sridhar et al. (2012[Sridhar, P. R., Reddy, G. M. & Seshadri, K. (2012). Eur. J. Org. Chem. 31, 6228-6235.]); Das et al. (2012[Das, S., Mishra, A. K., Kumar, A., Al Ghamdi, A. A. & Yadav, J. S. (2012). Carbohydr. Res. 358, 7-11.]); Dhavale & Matin (2005[Dhavale, D. D. & Matin, M. M. (2005). Arkivoc, pp. 110-132.]); Compain & Martin (2001[Compain, P. & Martin, O. R. (2001). Bioorg. Med. Chem. 9, 3077-3092.]); Derosa & Maffioli (2012[Derosa, G. & Maffioli, P. (2012). Arch. Med. Sci. 8, 899-906.]); Lew et al. (2000[Lew, W., Chen, X. & Kim, C. U. (2000). Curr. Med. Chem. 7, 663-672.]); Itzstein et al. (1993[Itzstein, M. von, Wu, W.-Y., Kok, G. B., Pegg, M. S., Dyason, J. C., Jin, B., Phan, T. V., Smythe, M. L., White, H. F., Oliver, S. W., Colman, P. M., Varghese, J. N., Ryan, D. M., Woods, J. M., Bethel, R. C., Hotham, V. J., Cameron, J. M. & Penn, C. R. (1993). Nature, 363, 418-423.]). For glycosidase inhibitors, see: Houston & Blanchfield (2003[Houston, T. A. & Blanchfield, J. T. (2003). Mini-Rev. Med. Chem. 3, 669-678.]). For iminosugars as glycosidase inhibitors, see: Zechel et al. (2003[Zechel, D. L., Boraston, A. B., Gloster, T., Boraston, C. M., Macdonald, J. M., Tilbrook, D. M. G., Stick, R. V. & Davies, G. J. (2003). J. Am. Chem. Soc. 125, 14313-14323.]); de Melo et al. (2006[Melo, E. B. de, Gomes, A. D. & Carvalho, I. (2006). Tetrahedron, 62, 10277-10302.]); Compain & Martin (2007[Compain, P. & Martin, O. R. (2007). Iminosugars: From Synthesis to Therapeutic Applications, ch. 9. Chichester: John Wiley and Sons Ltd.]). For examples of the clinical uses of iminosugars, see: Cox et al. (2003[Cox, T. M., et al. (2003). J. Inh. Met. Dis. 26, 513-526.]); Venier et al. (2012[Venier, R. E. & Igdoura, S. A. (2012). J. Med. Gen. 49, 591-597.]); Derosa & Maffioli (2012[Derosa, G. & Maffioli, P. (2012). Arch. Med. Sci. 8, 899-906.]). For iminosugars in the treatment of cancer, cystic fibrosis and viral diseases, see: Nishimura (2003[Nishimura, Y. (2003). Curr. Top. Med. Chem. 3, 575-591.]); Lawton & Witty (2011[Lawton, G. & Witty, D. R. (2011). Progress in Medicinal Chemistry, ch. 4. Amsterdam: Elsevier.]); Best, Jenkinson et al. (2010[Best, D., Jenkinson, S. F., Saville, A. W., Alonzi, D. S., Wormald, M. R., Butters, T. D., Norez, C., Becq, F., Blériot, Y., Adachi, I., Kato, A. & Fleet, G. W. J. (2010). Tetrahedron Lett. 51, 4170-4174.]); Compain & Martin (2007[Compain, P. & Martin, O. R. (2007). Iminosugars: From Synthesis to Therapeutic Applications, ch. 9. Chichester: John Wiley and Sons Ltd.]); Pollock et al. (2008[Pollock, S., Dwek, R. A., Burton, D. R. & Zitzmann, N. (2008). Aids, 22, 1961-1969.]). For the syntheses of DNJ and its analogues from L-sorbose, see: Beaupere et al. (1989[Beaupere, D., Stasik, B., Uzan, R. & Demailly, G. (1989). Carbohydr. Res. 191, 163-166.]); Masson et al. (2000[Masson, G., Compain, P. & Martin, O. R. (2000). Org. Lett. 2, 2971-2974.]); Tamayo et al. (2010[Tamayo, J. A., Franco, F. & Lo Re, D. (2010). Synlett, 9, 1323-1326.]); O'Brien & Murphy (2011[O'Brien, C. & Murphy, P. V. (2011). J. Carbohydr. Res. 30, 626-640.]). For the synthesis of 1-O-benzoyl-2,3-O-isopropylidene-6-O-tosyl-[alpha]-L-sorbofuranose, which bears structural similarity to the title compound, see: Fehér & Vargha (1966[Fehér, O. & Vargha, L. (1966). Acta. Chim. Acad. Sci. Hung. 50, 371-375.]).

[Scheme 1]

Experimental

Crystal data
  • C23H28O8S

  • Mr = 464.51

  • Monoclinic, C 2

  • a = 22.6192 (3) Å

  • b = 5.5649 (1) Å

  • c = 19.0631 (3) Å

  • [beta] = 104.696 (2)°

  • V = 2321.04 (6) Å3

  • Z = 4

  • Cu K[alpha] radiation

  • [mu] = 1.64 mm-1

  • T = 150 K

  • 0.29 × 0.06 × 0.02 mm

Data collection
  • Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.628, Tmax = 1.000

  • 24544 measured reflections

  • 4672 independent reflections

  • 4541 reflections with I > 2[sigma](I)

  • Rint = 0.031

Refinement
  • R[F2 > 2[sigma](F2)] = 0.044

  • wR(F2) = 0.127

  • S = 1.16

  • 4672 reflections

  • 293 parameters

  • 1 restraint

  • H-atom parameters constrained

  • [Delta][rho]max = 0.48 e Å-3

  • [Delta][rho]min = -0.27 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2165 Friedel pairs

  • Flack parameter: 0.000 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O3-H3O...O4i 0.84 1.98 2.812 (2) 174
Symmetry code: (i) x, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999[Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115-119.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Xtal3.6 (Hall et al., 1999[Hall, S. R., du Boulay, D. J. & Olthof-Hazekamp, R. (1999). Editors. Xtal3.6. University of Western Australia, Australia.]), ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA.]), SHELXLE (Hübschle et al., 2011[Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: publCIF (Westrip, (2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5615 ).


Acknowledgements

The University of Sydney is gratefully acknowledged for funding.

References

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Beaupere, D., Stasik, B., Uzan, R. & Demailly, G. (1989). Carbohydr. Res. 191, 163-166.  [CrossRef] [ChemPort] [Web of Science]
Best, D., Jenkinson, S. F., Saville, A. W., Alonzi, D. S., Wormald, M. R., Butters, T. D., Norez, C., Becq, F., Blériot, Y., Adachi, I., Kato, A. & Fleet, G. W. J. (2010). Tetrahedron Lett. 51, 4170-4174.  [Web of Science] [CrossRef] [ChemPort]
Best, D., Wang, C., Weymouth-Wilson, A. C., Clarkson, R. A., Wilson, F. X., Nash, R. J., Miyauchi, S., Kato, A. & Fleet, G. W. J. (2010). Tetrahedron Asymmetry, 21, 311-319.  [Web of Science] [CrossRef] [ChemPort]
Cipolla, L., La Ferla, B. & Nicotra, F. (2003). Curr. Top. Med. Chem. 3, 485-511.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
Compain, P., Chagnault, V. & Martin, O. R. (2009). Tetrahedron Asymmetry, 20, 672-711.  [Web of Science] [CrossRef] [ChemPort]
Compain, P. & Martin, O. R. (2001). Bioorg. Med. Chem. 9, 3077-3092.  [CrossRef] [PubMed] [ChemPort]
Compain, P. & Martin, O. R. (2007). Iminosugars: From Synthesis to Therapeutic Applications, ch. 9. Chichester: John Wiley and Sons Ltd.
Cox, T. M., et al. (2003). J. Inh. Met. Dis. 26, 513-526.  [CrossRef] [ChemPort]
Das, S., Mishra, A. K., Kumar, A., Al Ghamdi, A. A. & Yadav, J. S. (2012). Carbohydr. Res. 358, 7-11.  [Web of Science] [CrossRef] [ChemPort] [PubMed]
Derosa, G. & Maffioli, P. (2012). Arch. Med. Sci. 8, 899-906.  [CrossRef] [ChemPort] [PubMed]
Dhavale, D. D. & Matin, M. M. (2005). Arkivoc, pp. 110-132.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Fehér, O. & Vargha, L. (1966). Acta. Chim. Acad. Sci. Hung. 50, 371-375.
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [IUCr Journals]
Hall, S. R., du Boulay, D. J. & Olthof-Hazekamp, R. (1999). Editors. Xtal3.6. University of Western Australia, Australia.
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Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281-1284.  [Web of Science] [CrossRef] [IUCr Journals]
Itzstein, M. von, Wu, W.-Y., Kok, G. B., Pegg, M. S., Dyason, J. C., Jin, B., Phan, T. V., Smythe, M. L., White, H. F., Oliver, S. W., Colman, P. M., Varghese, J. N., Ryan, D. M., Woods, J. M., Bethel, R. C., Hotham, V. J., Cameron, J. M. & Penn, C. R. (1993). Nature, 363, 418-423.  [PubMed] [Web of Science]
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Lenagh-Snow, G. M. J., Araujo, N., Jenkinson, S. F., Rutherforf, C., Nakagawa, S., Kato, A., Yu, C.-Y., Weymouth-Wilson, A. C. & Fleet, G. W. J. (2011). Org. Lett. 13, 5834-5837.  [Web of Science] [ChemPort] [PubMed]
Lew, W., Chen, X. & Kim, C. U. (2000). Curr. Med. Chem. 7, 663-672.  [CrossRef] [PubMed] [ChemPort]
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Masson, G., Compain, P. & Martin, O. R. (2000). Org. Lett. 2, 2971-2974.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
Melo, E. B. de, Gomes, A. D. & Carvalho, I. (2006). Tetrahedron, 62, 10277-10302.
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Nishimura, Y. (2003). Curr. Top. Med. Chem. 3, 575-591.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
O'Brien, C. & Murphy, P. V. (2011). J. Carbohydr. Res. 30, 626-640.  [ChemPort]
Pollock, S., Dwek, R. A., Burton, D. R. & Zitzmann, N. (2008). Aids, 22, 1961-1969.  [CrossRef] [PubMed] [ChemPort]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Simone, M. I., Soengas, R. G., Jenkinson, S. F., Evinson, E. L., Nash, R. J. & Fleet, G. W. J. (2012). Tetrahedron Asymmetry, 23, 401-408.  [Web of Science] [CrossRef] [ChemPort]
Soengas, R. G., Simone, M., Hunter, S., Nash, R. J. & Fleet, G. W. J. (2012). Eur. J. Org. Chem. 12, 2394-2402.  [CrossRef]
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Tamayo, J. A., Franco, F. & Lo Re, D. (2010). Synlett, 9, 1323-1326.  [Web of Science] [CrossRef]
Venier, R. E. & Igdoura, S. A. (2012). J. Med. Gen. 49, 591-597.  [CrossRef] [ChemPort]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Wilkinson, B. L., Bornaghi, L. F., Lopez, M., Poulsen, S.-A., Healy, P. C. & Houston, T. A. (2010). Aust. J. Chem. 63, 821-829.  [Web of Science] [CSD] [CrossRef] [ChemPort]
Zechel, D. L., Boraston, A. B., Gloster, T., Boraston, C. M., Macdonald, J. M., Tilbrook, D. M. G., Stick, R. V. & Davies, G. J. (2003). J. Am. Chem. Soc. 125, 14313-14323.  [Web of Science] [CrossRef] [PubMed] [ChemPort]
Zhang, Z.-X., Wu, B., Wang, B., Li, T.-H., Zhang, P.-F., Guo, L.-N., Wang, W.-J., Zhao, W. & Wang, P. G. (2011). Tetrahedron Lett. 52, 3802-3805.  [Web of Science] [CSD] [CrossRef] [ChemPort]


Acta Cryst (2013). E69, o1069-o1070   [ doi:10.1107/S1600536813015638 ]

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