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

K. V. Radhakrishnan; V. S. Sajisha; Jessy Maria Chacko

doi:10.1055/s-2005-864818

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Synlett 2005(6): 0997-0999
DOI: 10.1055/s-2005-864818

LETTER

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

K. V. Radhakrishnan*, V. S. Sajisha, Jessy Maria Chacko
Organic Chemistry Section, Chemical Sciences Division, Regional Research Laboratory (CSIR), Trivandrum 690519, India
Fax: +91(471)2491712; e-Mail: radhupreethi@rediffmail.com;

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Publication History

Received 12 December 2004
Publication Date:
23 March 2005 (online)

Abstract
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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.

Key words

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

References

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18

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.