A Facile and Eco-Friendly Method for the Synthesis of 1,2-Orthoesters of Carbohydrates in Ionic Liquid

Abstract

A facile method for the synthesis of 1,2-orthoesters of carbohydrates in ionic liquid [bmim]PF₆ is described. The method described herein is simpler, eco-friendly and avoids the addition of quaternary ammonium salts as promoters.

ionic liquid - 1,2-orthoesters - carbohydrates - glycosyl bromides - quaternary ammonium salts

References

<A NAME="RD37204ST-1A">1a</A> Ionic Liquids in Synthesis   Wasserscheid P. Welton T. Wiley-VCH; Weinheim: 2002. 

<A NAME="RD37204ST-1B">1b</A> Leveque JM. Luche JL. Pefrier C. Roux R. Bonrath K. Green Chem.  2002,  357 

Recent reviews on ionic liquids:

<A NAME="RD37204ST-2A">2a</A> Dupont J. de Souza RF. Suarez PAZ. Chem. Rev.  2002,  102:  3667 

<A NAME="RD37204ST-2B">2b</A> Zhao H. Malhotra SV. Aldrichimica Acta  2002,  35:  75 

<A NAME="RD37204ST-2C">2c</A> Zhao D. Wu M. Kou Y. Min E. Catal. Today  2002,  74:  157 

<A NAME="RD37204ST-2D">2d</A> Olivier-Bourbigou H. Magna L. J. Mol. Catal. A.: Chem.  2002,  182-183:  419 

<A NAME="RD37204ST-2E">2e</A> Sheldon R. Chem. Commun.  2001,  2399 

<A NAME="RD37204ST-2F">2f</A> Gordon CM. Appl. Catal. A  2001,  222:  101 

<A NAME="RD37204ST-2G">2g</A> Earle MJ. Seddon KR. Pure Appl. Chem.  2000,  72:  1391 

<A NAME="RD37204ST-2H">2h</A> Wasserscheid P. Keim W. Angew. Chem. Int. Ed.  2000,  39:  3773 

<A NAME="RD37204ST-2I">2i</A> Welton T. Chem. Rev.  1999,  99:  2071 

<A NAME="RD37204ST-3">3</A> Glycoscience, Chemistry and Chemical Biology   Vol 1-III:  Fraser-Reid BF. Tatsuta K. Thiem J. Springer; Heidelberg: 2001. 

<A NAME="RD37204ST-4A">4a</A> Imperiali B. Acc. Chem. Res.  1997,  30:  452 

<A NAME="RD37204ST-4B">4b</A> Kevin JY. Carolyn RB. Curr. Opin. Chem. Biol.  1998,  2:  49 

<A NAME="RD37204ST-4C">4c</A> Bovin NV. Gabius HJ. Chem. Soc. Rev.  1995,  24:  413 

<A NAME="RD37204ST-4D">4d</A> Rye PD. Bovin NV. Glycobiology  1997,  7:  179 

<A NAME="RD37204ST-4E">4e</A> Sears P. Wong C.-H. Angew. Chem. Int. Ed.  1999,  38:  2300 

<A NAME="RD37204ST-4F">4f</A> Wirczak ZJ. Curr. Med. Chem.  1999,  6:  165 

<A NAME="RD37204ST-4G">4g</A> Carbohydrates in Chemistry and Biology   Ernst B. Hart GW. Sinay P. Wiley-VCH; Weinheim: 2000. 

<A NAME="RD37204ST-4H">4h</A> Maeder T. Sci. Amer.  2002,  287:  24 

<A NAME="RD37204ST-5">5</A> Murugesan S. Karst N. Islam T. Wiencek JM. Linhardt RJ. Synlett  2003,  13:  1283 

<A NAME="RD37204ST-6">6</A> Pakulski Z. Synlett  2003,  13:  2074 

<A NAME="RD37204ST-7">7</A> Pindur U. In The Chemistry of Acid Derivatives   Vol. 2:  Patai S. Wiley; New York: 1992.  p.967 

<A NAME="RD37204ST-8A">8a</A> Backinowsky LV. Nepogod’ev SA. Shashkov AS. Kochetkov NK. Carbohydr. Res.  1985,  138:  41 

<A NAME="RD37204ST-8B">8b</A> Vliegenthart JFG. Carbohydr. Res.  1977,  59:  81 

<A NAME="RD37204ST-8C">8c</A> Hatanaka K. Kuzahara H. J. Carbohydr. Chem.  1985,  4:  333 

<A NAME="RD37204ST-9A">9a</A> Jayaprakash KN. Radhakrishnan KV. Fraser-Reid B. Tetrahedron Lett.  2002,  43:  6955 

<A NAME="RD37204ST-9B">9b</A> Lu J. Fraser-Reid B. Org Lett.  2004,  6:  3051 

<A NAME="RD37204ST-9C">9c</A> Jayaprakash KN. Fraser-Reid B. Synlett  2004,  2:  301 

<A NAME="RD37204ST-10A">10a</A> Jayaprakash KN. Lu J. Fraser-Reid B. Bioorg. Med. Chem. Lett.  2004,  14:  3815 

<A NAME="RD37204ST-10B">10b</A> Lu J. Jayaprakash KN. Schlueter U. Fraser-Reid B. J. Am. Chem. Soc.  2004,  126:  7540 

<A NAME="RD37204ST-11">11</A> Pindur U. Muller J. Flo C. Witzel H. Chem. Soc. Rev.  1987,  16:  75 

<A NAME="RD37204ST-12A">12a</A> Gorin PAJ. Carbohydr. Res.  1982,  101:  12 

<A NAME="RD37204ST-12B">12b</A> Trumtel M. Veyriere A. Sinay P. Tetrahedron Lett.  1989,  30:  2529 

<A NAME="RD37204ST-12C">12c</A> Trumtel M. Tavecchia P. Veyriere A. Sinay P. Carbohydr. Res.  1989,  191:  29 

<A NAME="RD37204ST-13">13</A> Lemieux RU. Morgan AR. Can. J. Chem.  1965,  43:  2199 

<A NAME="RD37204ST-14">14</A> Wang W. Kong F. J. Org. Chem.  1998,  63:  5744 

<A NAME="RD37204ST-15">15</A> Shoda S. Moteki M. Izumi R. Noguchi M. Tetrahedron Lett.  2004,  45:  8847 

<A NAME="RD37204ST-16">16</A> Ernst B. Mesmaeker AD. Wagner B. Winkler T. Tetrahedron Lett.  1990,  31:  6167 

<A NAME="RD37204ST-17A">17a</A> Roberts C. Madsen R. Fraser-Reid B. J. Am. Chem. Soc.  1995,  117:  1546 

<A NAME="RD37204ST-17B">17b</A> Preparative Carbohydrate Chemistry   Hanessian S. Marcel Dekker, Inc.; New York: 1997. 

<A NAME="RD37204ST-18">18</A>

Spectral data for some key compounds.
(a) 3,4,6,-Tri- O -benzoyl Glucopyranosyl n -Pentenyl Orthoester: R _f = 0.2926 (25% EtOAc-hexane). IR (neat): ν_max = 3070, 2449, 1740, 1644, 1612, 1460, 1275, 1109, 976, 925, 708 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.24-8.60 (m, 20 H), 6.01 (d, 1 H, J = 5.2 Hz), 5.84-5.67 (m, 1 H), 5.47 (d, 1 H, J = 8.7 Hz), 4.97 (d, 1 H, J = 1.5 Hz), 4.92 (d, 1 H, J = 1.3 Hz), 4.74 (dd, 1 H, J = 3.4, 7.2 Hz), 4.51 (dd, 1 H, J = 4.8, 12.0 Hz), 3.29-3.37 (m, 2 H), 2.01-2.09 (m, 2 H), 1.57-1.62 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 165.68, 164.95, 164.39, 137.68, 135.51, 133.49, 133.32, 132.80, 129.98, 129.85, 129.68, 129.69, 129.46, 129.14, 129.03, 128.46, 128.33, 128.19, 128.10, 126.28, 121.19, 120.02, 114.97, 97.42, 72.08, 69.23, 68.48, 67.42, 63.89, 63.29, 30.10, 28.60.
(b) 3,4,6-Tri- O -benzoyl Galactopyranosyl Allyl Orthoester: R _f = 0.2954 (25% EtOAc-hexane). IR (neat): ν_max = 2917, 2366, 1721, 1452, 1263, 1086, 708 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.35-7.97 (m, 20 H), 6.21 (d, 1 H, J = 5.03 Hz), 5.92-5.80 (m, 1 H), 5.56 (dd, 1 H, J = 4.26, 5.06 Hz), 5.12 (d, 2 H, J = 10.45 Hz), 4.79 (dd, 1 H, J = 7.14, 12.35 Hz), 4.64-4.50 (m, 1 H), 4.38 (dd, 1 H, J = 4.93, 10.60 Hz), 3.93 (d, 2 H, J = 4.87 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 165.18, 164.91, 164.28, 136.29, 133.78, 133.51, 133.35, 133.13, 129.81, 129.78, 129.73, 129.63, 129.42, 129.11, 128.92, 128.49, 128.35, 128.31, 126.09, 125.98, 120.31, 116.70, 98.55, 98.21, 73.41, 70.09, 68.88, 66.47, 64.96, 62.35, 29.68.
(c) 3,4,6-Tri- O -benzoyl Mannopyranosyl Isopropyl Orthoester: R _f = 0.2973 (25% EtOAc-hexane). IR (neat): ν_max = 2917, 2849, 2356, 1716, 1458, 1269, 1086 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.23-8.01 (m, 20 H), 5.74 (d, 1 H, J = 2.98 Hz), 5.62 (dd, 1 H, J = 3.64, 9.97 Hz), 5.04 (t, 1 H, J = 3.4 Hz), 4.47 (dd, 1 H, J = 3.40, 11.99 Hz), 4.31 (dd, 1 H, J = 4.84, 11.97 Hz), 3.73 (m, 1 H), 1.07 (d, 3 H, J = 6.12 Hz), 1.03 (d, 3 H, J = 6.12 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 165.78, 165.70, 165.03, 145.37, 137.35, 133.36, 133.26, 132.79, 130.11, 129.91, 129.82, 129.23, 129.18, 128.44, 128.41, 128.23, 128.07, 126.61, 124.29, 123.57, 123.03, 119.16, 97.90, 75.73, 72.41, 71.18, 67.35, 66.77, 63.28, 23.51, 23.43.