A Facile H₂SO₄/4 Å Molecular Sieves Catalyzed Synthesis of 2,3-Unsaturated O-Glycosides via Ferrier-Type Rearrangement

Abstract

A novel method for synthesizing 2,3-unsaturated glycosides has been developed using a metal-free catalytic system. This catalyst, sulfuric acid/4 Å molecular sieves can catalyze the reaction of 3,4,6-tri-O-acetyl-d-glucals and a wide range of alcohols at room temperature, affording 2,3-unsaturated glycosides in good α-selectivity (α/β > 6:1) via a Ferrier-type rearrangement.

Key words

Ferrier rearrangement - sulfuric acid - molecular sieves - d-glucal - O-glycosides - glycosylation

References and Notes

• 1a Ferrier RJ. Prasad N. J. Chem. Soc. C.  1969,  570 
• 1b Ferrier RJ. Adv. Carbohydr. Chem. Biochem.  1970,  24:  199 
• 1c Ferrier RJ. Top. Curr. Chem.  2001,  215:  153 
• 1d Ferrier RJ. Zubkov OA. Org. React.  2003,  62:  569 ; and references therein
• 2a Fraser-Reid B. Acc. Chem. Res.  1985,  18:  347 
• 2b Tolstikov AG. Tolstikov GA. Russ. Chem. Rev.  1993,  62:  579 
• 2c Li JJ. Name Reactions   3rd ed.:  Springer; Berlin: 2002.  p.119 
• 2d Zhang J. Glycoscience   2nd ed.:  Fraser-Reid B. Tatsuta K. Thiem J. Springer; Heidelberg: 2008.  p.375 
• 3a Schreiber SL. Science  2000,  287:  1964 
• 3b Kubota H. Lim J. Depew KM. Schreiber SL. Chem. Biol.  2002,  9:  265 
• 3c Burke MD. Berger EM. Schreiber SL. Science  2003,  302:  613 
• 3d Hotha S. Tripathi A.
  J. Comb. Chem.  2005,  7:  968 
• 4a Schmidt RR. Angerbauer R. Carbohydr. Res.  1979,  72:  272 
• 4b Dorgan BJ. Jackson RFW. Synlett  1996,  859 
• 5 Wieczorek E. Thiem J. Polish J. Chem.  1999,  73:  1111 
• 6a Schmidt RR. Angerbauer R. Carbohydr. Res.  1981,  89:  159 
• 6b Angerbauer R. Schmidt RR. Carbohydr. Res.  1981,  89:  193 
• 7a Schmidt RR. Angerbauer R. Angew. Chem., Int. Ed. Engl.  1977,  16:  783 
• 7b Yadav JS. Reddy BVS. Synthesis  2002,  511 
• 8 Kartika R. Frein JD. Taylor RE. J. Org. Chem.  2008,  73:  5592 
• 9a Schmidt RR. Angerbauer R. Carbohydr. Res.  1979,  72:  272 
• 9b Bracherro MP. Cabrera EF. Gomez GM. Peredes LMR. Carbohydr. Res.  1998,  308:  181 
• 10a Stevens CL. Filippi JB. Taylor KG. J. Org. Chem.  1966,  31:  1292 
• 10b Isobe M. Ichikawa Y. Funabashi Y. Mio S. Goto T. Tetrahedron  1986,  42:  2863 
• 10c Chapleur Y. Moufid N. J. Chem. Soc., Chem. Commun.  1989,  39 
• 10d Marco-Contelles J. Tetrahedron Lett.  1994,  35:  5059 
• 10e Jiang Y. Ichikawa Y. Isobe M. Synlett  1995,  285 
• 10f Banaag AR. Tius MA. J. Org. Chem.  2008,  73:  8133 
• 10g Fernandes A. DellOlmo M. Tatibouet A. Imberty A. Philouze C. Rollin P. Tetrahedron Lett.  2008,  49:  3484 
• 11a Grynkiewiez G. Priebe W. Zamojski A. Carbohydr. Res.  1979,  68:  33 
• 11b Bhate P. Horton D. Priebe W. Carbohydr. Res.  1985,  144:  331 
• 12a Babu BS. Balasubramanian KK. Tetrahedron Lett.  2000,  41:  1271 
• 12b Nagaraj P. Ramesh NG. Tetrahedron Lett.  2009,  50:  3970 
• 13 Yadav JS. Reddy BV. Murthy CV. Kumar GM. Synlett  2000,  1450 
• 14 Masson C. Soto J. Bessodes M. Synlett  2000,  1281 
• 15 Takhi M. Rahman A. Adel AH. Schmidt RR. Tetrahedron Lett.  2001,  42:  4053 
• 16 Babu BS. Balasubramnaian KK. Synth. Commun.  1998,  29:  4299 
• 17 Yadav JS. Reddy BV. Reddy JS. J. Chem. Soc., Perkin Trans. 1  2002,  2390 
• 18 Swamy NR. Venkateswarlu A. Synthesis  2002,  598 
• 19 Bettadaiah BK. Srinivas P. Tetrahedron Lett.  2003,  44:  7257 
• 20a Banik BK. Adler D. Nguyen P. Srivastava N. Heterocycles  2003,  61:  101 
• 20b Naik PU. Nara SJ. Harjani JR. Salunkhe MM. J. Mol. Catal. A: Chem.  2005,  234:  35 
• 21 Smitha G. Reddy SC. Synthesis  2004,  834 
• 22 Agarwal A. Rani S. Vankar YD. J. Org. Chem.  2004,  69:  6137 
• 23 Hotha S. Tripathi A. Tetrahedron Lett.  2005,  46:  4555 
• 24 Zhang G. Liu Q. Shi L. Wang J. Tetrahedron  2008,  64:  339 
• 25 Gorityala BK. Lorpitthaya R. Bai Y. Liu XW. Tetrahedron Lett.  2009,  65:  5844 
• 26a Kaczmarek J. Preyss M. Liinnberg H. Szafranek J. Carbohydr. Res.  1995,  279:  107 
• 26b Kaczmarek J. Kaczynski Z. Trumpakaj Z. Szafranek J. Bogalecka M. Lonnberg H. Carbohydr. Res.  2000,  325:  16 
• 26c Chao CS. Chen MC. Lin SC. Mong KKT. Carbohydr. Res.  2008,  343:  957 
• 27 Oberdorfer and co-workers have demonstrated similar Ferrier rearrangement using d-galactal for the construction of the (2R)-2-hydroxy-6,8-dioxabicyclo[3.2.1]oct-3-ene via an intramolecular pathway in 40% yield: Oberdorfer F. Haeckel R. Lauer G. Synthesis  1998,  201 
• 28 Boga SB. Balasubramanian KK. ARKIVOC  2004,  (viii):  87 
• 29 Naik PU. Nara SJ. Harjani JR. Salunkhe MM. J. Mol. Catal. A: Chem.  2005,  234:  35 
• 30a Tilve RD. Alexander MV. Khandekar AC. Samant SD. Kanetkar VR. J. Mol. Catal. A: Chem.  2004,  223:  237 
• 30b Roy SC, Lesley SJ, Dilek S, and Nino M. inventors; WO  2005070911. 
• 31 Surya Kiran N. Malla Reddy S. Srinivasulu M. Venkateswarlu Y. Synth. Commun.  2008,  38:  170 
• 32 Swami NR. Venkateswarlu A. Synthesis  2002,  598 

33

General Experimental Procedure
Typically, H₂SO₄ (0.3 equiv, 16 mL) was added to the mixture of d-glucal (1 mmol, 272 mg), 4 Å MS (272 mg) and alcohol (1.5 equiv) in CH₂Cl₂, and the reaction mixture was stirred for 5 min at r.t. After the reaction was completed, the reaction mixture was filtered and washed with CH₂Cl₂. The combined organic layer was washed with sat. NaHCO₃ solution (10 mL) and sat. brine (10 mL), and then dried over anhyd Na₂SO₄. After evaporation of the solvent under reduced pressure, the crude products were purified by silica gel column chromatography (PE-EtOAc = 10:1).

34

Selected Spectral Data
n -Pentyl 4,6-Di- O -acetyl-2,3-dideoxy-a- d - erythro -hex-2-enopyranoside (5b)
^¹H NMR (500 MHz, CDCl₃): d = 0.91 (t, J = 6.7 Hz, 3 H), 1.34-1.37 (m, 4 H), 1.59-1.63 (m, 2 H), 2.07-2.10 (m, 6 H), 3.48-3.53 (m, 1 H), 3.75-3.80 (m, 1 H), 4.09-4.27 (m, 3 H, H-5, H-6a, H-6b), 5.03 (s, 1 H, H-1), 5.30-5.32 (dd, 1 H, J = 9.6 Hz, H-4), 5.83-5.89 (m, 2 H, H-2, H-3) ppm. ^¹³C NMR (125 MHz, CDCl₃): d = 13.94, 20.69, 20.88, 22.40, 28.31, 29.32, 62.99, 65.27, 66.81, 68.87, 94.31, 127.92, 128.89, 170.22, 170.71 ppm. ESI-MS: m/z = 323.10 [M + Na⁺].
n -Decyl 4,6-Di- O -acetyl-2,3-dideoxy-a- d - erythro -hex-2-enopyranoside (6b)
^¹H NMR (500 MHz, CDCl₃): d = 0.86 (t, 3 H), 1.26-1.35 (m, 16 H), 2.07-2.09 (m, J = 9.2 Hz, 6 H), 3.49 (m, 1 H), 4.09-4.26 (m, 3 H, H-5, H-6a, H-6b), 5.01 (s, 1 H, H-1), 5.29-5.32 (dd, J = 1.3, 9.7 Hz, 1 H, H-4), 5.83-5.88 (m, 2 H, H-2, H-3) ppm. ^¹³C NMR (125 MHz, CDCl₃): d = 14.00, 20.69, 20.87, 22.58, 25.67, 26.16, 29.23, 29.36, 29.47, 31.81, 32.70, 62.92, 64.37, 66.80, 68.94, 94.32, 127.90, 128.88, 170.27, 170.76 ppm. ESI-MS: m/z = 393.20 [M + Na⁺].
2-Ethylhexyl 4,6-Di- O -acetyl-2,3-dideoxy-a- d - erythro -hex-2-enopyranoside (12b)
^¹H NMR (500 MHz, CDCl₃): d = 0.86-0.91 (m, 6 H), 1.26-1.33 (m, 8 H), 1.34-1.42 (m, 1 H), 2.09-2.10 (m, J = 5.7 Hz, 6 H), 3.36-3.38 (q, 1 H), 3.54-3.55 (d, 1 H), 3.70-3.71 (t, 1 H), 4.08-4.25 (m, 3 H, H-5, H-6a, H-6b), 5.00 (s, 1 H, H-1), 5.29-5.31 (dd, J = 9.7 Hz, 1 H, H-4), 5.82-5.94 (m, 2 H, H-2, H-3) ppm. ^¹³C NMR (125 MHz, CDCl₃): d = 11.02, 13.99, 20.67, 20.87, 22.94, 23.68, 28.93, 30.49, 39.57, 63.03, 65.28, 66.87, 72.64, 94.45-94.53, 127.95, 128.74, 170.21, 170.71 ppm. ESI-MS: m/z = 365.14 [M + Na⁺].
2-Cyanoethyl 4,6-Di- O -acetyl-2,3-dideoxy-a- d - erythro -hex-2-enopyranoside (15b)
^¹H NMR (500 MHz, CDCl₃): d = 2.08-2.10 (m, J = 10.0 Hz, 6 H), 2.64-2.71 (m, 2 H), 3.76-3.97 (m, 2 H), 4.12-4.22 (m, 3 H, H-5, H-6a, H-6b), 5.07 (s, 1 H, H-1), 5.29-5.31 (dd, 1 H, J = 1.0, 9.5 Hz, H-4), 5.81-5.93 (m, 2 H, H-2, H-3) ppm. ^¹³C NMR (125 MHz, CDCl₃): d = 18.96, 20.56, 20.72, 62.69, 63.26, 64.85, 67.14, 94.60, 117.58, 126.70, 129.57, 170.13, 170.59 ppm. ESI-MS: m/z = 306.07 [M + Na⁺].
Trichloroethyl 4,6-Di- O -acetyl-2,3-dideoxy-a- d - erythro -hex-2-enopyranoside (17b)
^¹H NMR (500 MHz, CDCl₃): d = 2.07-2.13 (m, J = 10.8 Hz, 6 H), 4.17-4.18 (d, 2 H), 4.27-4.36 (m, 3 H, H-5, H-6a, H-6b), 5.31 (s, 1 H, H-1), 5.37-5.38 (dd, J = 9.2 Hz, 1 H, H-4), 5.97-6.00 (m, 2 H, H-2, H-3) ppm. ^¹³C NMR (125 MHz, CDCl₃): d = 20.76, 20.87, 62.66, 65.01, 67.49, 76.15, 79.61, 96.37, 126.38, 130.20, 170.39, 170.92 ppm. ESI-MS: m/z = 382.94 [M + Na⁺].