Synlett 2010(10): 1519-1524  
DOI: 10.1055/s-0029-1219943
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Direct α-Selective Glycosylations of Acetyl-Protected 2-Deoxy- and 2,6-Dideoxythioglycosides by Preactivation Protocol

Yin-Suo Lua,b, Qin Lia,b, Yuan Wanga,b, Xin-Shan Ye*a,b
a The State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd No. 38, Beijing 100191, P. R. of China
b School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd No. 38, Beijing 100191, P. R. of China
Fax: +86(10)62014949; e-Mail: xinshan@bjmu.edu.cn;
Further Information

Publication History

Received 4 March 2010
Publication Date:
19 May 2010 (online)

Abstract

An efficient preactivation protocol for the highly α-stereo­selective glycosylation of 2-deoxy- and 2,6-dideoxysugars has been developed using acetyl-protected 2-deoxy- and 2,6-dideoxythioglycosides as glycosyl donors. The approach allows a wide range of glycosyl acceptors and donors to be used.

    References and Notes

  • 1a Kirschning A. Bechthold AF.-W. Rohr J. Top. Curr. Chem.  1997,  188:  1 
  • 1b Weymouth-Wilson AC. Nat. Prod. Rep.  1997,  14:  99 
  • 1c Butler MS. J. Nat. Prod.  2004,  67:  2141 
  • 2a Tavecchia P. Trumtel M. Veyrieres A. Sinaÿ P. Tetrahedron Lett.  1989,  30:  2533 
  • 2b Perez M. Beau J.-M. Tetrahedron Lett.  1989,  30:  75 
  • 2c Roush WR. Bennett CE. J. Am. Chem. Soc.  1999,  121:  3541 
  • 2d Blanchard N. Roush WR. Org. Lett.  2003,  5:  81 
  • 2e Roush WR. Sebesta DP. James RA. Tetrahedron  1997,  53:  8837 
  • 2f Thiem J. Schottmer B. Angew. Chem., Int. Ed. Engl.  1987,  26:  555 
  • 2g Marzabadi CH. Franck RW. Tetrahedron  2000,  56:  8385 
  • 3a Nicolaou KC. Ladduwahetty T. Randall JL. Chucholowski A. J. Am. Chem. Soc.  1986,  108:  2466 
  • 3b Zuurmond HM. van der Klein PAM. van der Marel GA. van Boom JH. Tetrahedron Lett.  1992,  33:  2063 
  • 4 Toshima K. Mukaiyama S. Nozaki Y. Inokuchi H. Nakata M. Tatsuta K. J. Am. Chem. Soc.  1994,  116:  9042 
  • 5 Rodríguez MA. Boutureira O. Matheu MI. Díaz Y. Castillón S. Eur. J. Org. Chem.  2007,  2470 
  • 6a Lemieux RU. Morgan AR. Can. J. Chem.  1964,  42:  1473 
  • 6b Muller T. Schneider R. Schmidt RR. Tetrahedron Lett.  1994,  35:  4763 
  • 7 Binkley RW. Koholic DJ. J. Org. Chem.  1989,  54:  3577 
  • 8 Tanaka H. Yoshizawa A. Takahashi T. Angew. Chem. Int. Ed.  2007,  46:  2505 
  • 9 Lear MJ. Yoshimura F. Hirama M. Angew. Chem. Int. Ed.  2001,  40:  946 
  • 10 Jaunzems J. Sourkouni-Argirusi G. Jesberger M. Kirschning A. Tetrahedron Lett.  2003,  44:  637 
  • 11 Toshima K. Nozaki Y. Tatsuta K. Tetrahedron Lett.  1991,  32:  6887 
  • 12a Bielawska H. Michalska M. J. Carbohydr. Chem.  1991,  10:  107 
  • 12b Laupichler L. Sajus H. Thiem J. Synthesis  1992,  1133 
  • 12c Mereyala HB. Kulkarni VR. Ravi D. Sharma GVM. Rao BV. Reddy GB. Tetrahedron  1992,  48:  545 
  • 13 Morris WJ. Shair MD. Org. Lett.  2009,  11: 
  • 14a Ito Y. Ogawa T. Tetrahedron Lett.  1987,  28:  2723 
  • 14b Li H. Chen M. Zhao K. Tetrahedron Lett.  1997,  38:  6143 
  • 14c Kim KS. Park J. Lee YJ. Seo YS. Angew. Chem. Int. Ed.  2003,  42:  459 
  • 15a Yadav JS. Reddy BVS. Reddy KB. Satyanarayana M. Tetrahedron Lett.  2002,  43:  7009 
  • 15b Sherry BD. Loy RN. Toste FD. J. Am. Chem. Soc.  2004,  126:  4510 
  • 16a Wang Y. Ye X.-S. Zhang L.-H. Org. Biomol. Chem.  2007,  5:  2189 
  • 16b Crich D. Sun S. J. Org. Chem.  1996,  61:  4506 
  • 16c Crich D. Sun S. J. Org. Chem.  1997,  62:  1198 
  • 16d Codée JDC. Van den Bos LJ. Litjens REJN. Overkleeft HS. Van Boom JH. Van der Marel GA. Org. Lett.  2003,  5:  1947 
  • 16e Yamago S. Yamada T. Maruyama T. Yoshida J.-I. Angew. Chem. Int. Ed.  2004,  43:  2145 
  • 16f Nguyen HM. Poole JL. Gin DY. Angew. Chem. Int. Ed.  2001,  40:  414 
  • 16g Huang L. Wang Z. Li X. Ye X.-S. Huang X. Carbohydr. Res.  2006,  341:  1669 
  • 16h Huang L. Huang X. Chem. Eur. J.  2007,  13:  529 
  • 17 Huang X. Huang L. Wang H. Ye X.-S. Angew. Chem. Int. Ed.  2004,  43:  5221 
  • 18a Geng Y. Zhang L.-H. Ye X.-S. Chem. Commun.  2008,  597 
  • 18b Geng Y. Zhang L.-H. Ye X.-S. Tetrahedron  2008,  64:  4949 
  • For the use of oxazolidinone functionality, also see, for example:
  • 18c Benakli K. Zha C. Kerns RJ. J. Am. Chem. Soc.  2001,  123:  9461 
  • 18d Boysen M. Gemma E. Lahmann M. Oscarson S. Chem. Commun.  2005,  3044 
  • 18e Manabe S. Ishii K. Ito Y. J. Am. Chem. Soc.  2006,  128:  10666 
  • 19 Lu Y.-S. Li Q. Zhang L.-H. Ye X.-S. Org. Lett.  2008,  10:  3445 
  • For the use of carbonate functionality, also see, for example:
  • 20a Crich D. Jayalath P. J. Org. Chem.  2005,  70:  7252 
  • 20b Crich D. Vinod AU. Picione J. J. Org. Chem.  2003,  68:  8453 
  • 20c Cotarca L. Delogu P. Nardelli A. Sunjic V. Synthesis  1996,  553 
  • 21 Wang C. Wang H. Huang X. Zhang L.-H. Ye X.-S. Synlett  2006,  2846 
  • 23a Burgey CS. Vollerthun R. Fraser-Reid B. J. Org. Chem.  1996,  61:  1609 
  • 23b Mootoo DR. Konradsson P. Udodong U. Fraser-Reid B. J. Am. Chem. Soc.  1988,  110:  5583 
  • 24 Zhu T. Boons G.-J. Org. Lett.  2001,  3:  4201 ; and references cited therein
  • 25a Crich D. Sun S. Tetrahedron  1998,  54:  8321 
  • 25b Crich D. Smith M. J. Am. Chem. Soc.  2001,  123:  9015 
  • 25c Kim KS. Kim JH. Lee YJ. Lee YJ. Park J. J. Am. Chem. Soc.  2001,  123:  8477 
  • 25d Tanada S.-I. Takashima M. Tokimoto H. Fujimoto Y. Tanaka K. Fukase K. Synlett  2005,  2325 
  • 25e Codee JDC. Krock L. Castagner B. Seeberger PH. Chem. Eur. J.  2008,  14:  3987 
  • 25f Crich D. Sharma I. Org. Lett.  2008,  10:  4731 
  • 25g Crich D. Li L.-F. J. Org. Chem.  2009,  74:  773 ; and references cited therein
  • 26 Manabe S. Ishii K. Hashizume D. Koshino H. Ito Y. Chem. Eur. J.  2009,  15:  6894 
  • 27 Lin S.-C. Chao C.-S. Chang C.-C. Mong K.-KT. Tetrahedron Lett.  2010,  51:  1910 
  • 28 Park J. Boltje TJ. Boons G.-J. Org. Lett.  2008,  10:  4367 
  • 29 Xiong D.-C. Zhang L.-H. Ye X.-S. Adv. Synth. Catal.  2008,  350:  1696 ; and references cited therein
22

Typical Glycosylation Procedure
Triflic anhydride (11.0 µL, 0.061 mmol) was added to a stirred solution of p-methylphenyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-α-d-galactopyranoside (1a, 30.0 mg, 0.076 mmol), benzenesulfinyl morpholine (BSM, 12.9 mg, 0.061 mmol), and 4 Å MS (350 mg, activated powder) in CH2Cl2 (3.0 mL) at -72 ˚C under nitrogen atmosphere. The reaction mixture was stirred for 10 min. After loss of 1a detected by TLC, a solution of methyl 3-O-benzyl-4,6-O-benzylidene-α-d-glucopyranoside (2a, 18.8 mg, 0.051 mmol) in CH2Cl2 (0.5 mL) was added dropwise to the reaction mixture. The mixture was stirred for 30 min, and the reaction was quenched by Et3N (8.0 µL). The precipitate was filtered off, and the filtrate was concentrated. The residue was purified by column chromatography on silica gel (PE-EtOAc, 2.5:1) to give methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(3,4,6-tri-O-acetyl-2-deoxy-α-d-galactopyranosyl)-α-d-gluco-pyranoside (3a, 27.6 mg, 84% yield) as a foam. R f  = 0.35 (PE-EtOAc, 1.5:1). ¹H NMR (500 MHz, CDCl3): δ = 7.50 (dd, 2 H, J = 2.0, 7.5 Hz), 7.40-7.33 (m, 7 H), 7.29-7.27 (m, 1 H), 5.60 (s, 1 H), 5.37 (ddd, 1 H, J = 3.0, 5.0, 12.5 Hz), 5.15 (d, 1 H, J = 3.0 Hz), 5.14 (d, 1 H, J = 3.5 Hz), 4.93 (d, 1 H, J = 10.5 Hz), 4.89 (d, 1 H, J = 3.5 Hz), 4.71 (d, 1 H, J = 10.5 Hz), 4.36 (t, 1 H, J = 6.5 Hz), 4.31 (dd, 1 H, J = 4.5, 10.0 Hz), 3.98 (t, 1 H, J = 9.5 Hz), 3.90 (dd, 1 H, J = 6.5, 11.0 Hz), 3.87-3.74 (m, 4 H), 3.65 (t, 1 H, J = 9.5 Hz), 3.43 (s, 3 H), 2.13-2.08 (m, 4 H), 2.00 (s, 3 H), 1.96-1.92 (m, 4 H). ¹³C NMR (125 MHz, CDCl3): δ = 170.13, 170.23, 169.79, 138.06, 137.26, 128.96, 128.54, 128.47, 128.25, 127.86, 125.95, 101.27, 97.12, 94.10, 82.71, 76.85, 75.74, 73.45, 69.00, 66.61, 65.87, 62.25, 61.87, 55.23, 29.86, 20.81, 20.70. MS (ESI-TOF, positive): m/z = 667 [M + Na]+. Anal. Calcd for C33H40O13: C, 61.48; H, 6.25. Found: C, 61.65; H, 6.40.