Regioselective Reductive Ring
Opening of Benzylidene Acetals Using Triethylsilane and
Iodine

Rajib Panchadhayee; Anup Kumar Misra

doi:10.1055/s-0029-1219798

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Synlett 2010(8): 1193-1196
DOI: 10.1055/s-0029-1219798

LETTER

Regioselective Reductive Ring Opening of Benzylidene Acetals Using Triethylsilane and Iodine

Rajib Panchadhayee, Anup Kumar Misra*
Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India
Fax: +91(33)23553886; e-Mail: akmisra69@gmail.com;

Further Information

Publication History

Received 22 January 2010
Publication Date:
23 March 2010 (online)

Abstract
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Supplementary Material

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Abstract

Novel reaction conditions have been developed for the regioselective reductive ring opening of benzylidene acetals in carbohydrate derivatives using triethylsilane and molecular iodine. The reaction is fast, compatible with most of the functional groups encountered in the oligosaccharide synthesis, and yields were excellent. The reaction conditions are equally effective in thioglycosides.

Key words

carbohydrate - benzylidene acetal - regioselective - iodine - triethylsilane

Supporting Information

References and Notes

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23

Spectroscopic data for novel products are presented below. To aid assignments, data were taken after acetylation of the products.
4-Methoxyphenyl 2,3,4-Tri- O -acetyl-6- O -benzyl-β- d -galactopyranoside (Acetylated 22)
^¹H NMR (500 MHz, CDCl₃): δ = 7.25-7.17 (m, 5 H, ArH), 6.87 (d, J = 9.0 Hz, 2 H, ArH), 6.70 (d, J = 9.0 Hz, 2 H, ArH), 5.40 (d, J = 3.3 Hz, 1 H, H-4), 5.31 (dd, J = 7.9 Hz each, 1 H, H-2), 4.99 (dd, J = 10.4, 3.4 Hz, 1 H, H-3), 4.83 (d, J = 7.9 Hz, 1 H, H-1), 4.48 (d, J = 11.9 Hz, 1 H, PhCH_2a), 4.36 (d, J = 11.9 Hz, 1 H, PhCH_2b), 3.87-3.84 (m, 1 H, H-5), 3.68 (s, 3 H, OCH₃), 3.52-3.44 (m, 2 H, H-6_a,b), 2.01, 1.99, 1.93 (3 s, 9 H, 3 COCH₃). ^¹³C NMR (125 MHz, CDCl₃): δ = 170.3, 170.1, 169.5 (3 COCH₃), 156.0-114.9 (ArC), 101.1 (C-1), 73.9, 72.9, 71.5, 69.4, 67.9, 67.8, 55.8, 21.1, 21.0, 20.9 (3 COCH₃). ESI-MS (C₂₆H₃₀O₁₀): m/z = 525.1 [M + Na]⁺.
Phenyl 2,3,4-Tri- O -acetyl-6- O -benzyl-1-seleno-β-d-glucopyranoside (Acetylated 25) ^¹H NMR (500 MHz, CDCl₃): δ = 7.59-7.21 (m, 10 H, ArH), 5.15 (t, J = 9.2 Hz, 1 H, H-3), 5.01 (t, J = 9.8 Hz, 1 H, H-2), 4.97 (t, J = 9.2 Hz, 1 H, H-4), 4.88 (d, J = 9.9 Hz, 1 H, H-1), 4.53-4.46 (2 d, J = 11.8 Hz, 2 H, PhCH₂), 3.67-3.63 (m, 1 H, H-5), 3.56-3.54 (m, 2 H, H-6_a,b), 2.14, 2.05, 1.96 (3 s, 9 H, 3 COCH₃). ^¹³C NMR (125 MHz, CDCl₃): δ = 170.4, 169.6, 169.4 (3 COCH₃), 138.2-127.6 (ArC), 81.4 (C-1), 78.9, 74.4, 73.9, 71.3, 69.4 (2 C), 21.1, 20.9 (2 C) (3 COCH₃). ESI-MS (C₂₅H₂₈O₈Se): m/z = 559.1 [M + Na]⁺.
Methyl (2,3,4-Tri- O -acetyl-6- O -benzyl-β-d-glucopyranosyl)-(1→6)-2,3,4-tri- O -acetyl-α-d-glucopyranoside (Acetylated 26)
^¹H NMR (500 MHz, CDCl₃): δ = 7.33-7.24 (m, 5 H, ArH), 5.43 (t, J = 10.0 Hz each, 1 H, H-3_A), 5.16 (t, J = 9.4 Hz each, 1 H, H-4_A), 5.03 (t, J = 9.5 Hz each, 1 H, H-3_B), 4.96 (dd, J = 7.9 Hz each, 1 H, H-2_B), 4.90 (t, J = 9.4 Hz each, 1 H, H-4_B), 4.88 (d, J = 3.6 Hz, 1 H, H-1_A), 4.82 (dd, J = 10.1, 3.6 Hz, 1 H, H-2_A), 4.55 (d, J = 11.9 Hz, 1 H, PhCH_2a), 4.52 (d, J = 7.9 Hz, 1 H, H-1_B), 4.48 (d, J = 11.9 Hz, 1 H, PhCH_2b), 3.94-3.89 (m, 2 H, H-6_abA), 3.65-3.61 (m, 1 H, H-5_B), 3.55-3.51 (m, 3 H, H-5_A, H-6_a,bB), 3.37 (s, 3 H, OCH₃), 2.06, 2.03, 1.98, 1.89 (4 s, 18 H, 6 COCH₃). ^¹³C NMR (125 MHz, CDCl₃): δ = 170.4, 170.1, 170.0, 169.7, 169.6, 169.4 (6 COCH₃), 137.9-128.1 (ArC), 101.2 (C-1_B), 96.8 (C-1_A), 73.9, 73.7, 73.3, 71.6, 71.2, 70.6, 69.7, 69.4, 69.2, 68.5, 68.3, 55.5 (OCH₃), 21.1 (2 C), 21.0 (2 C), 20.9 (2 C). ESI-MS (C₃₀H₄₀O₁₆): m/z = 679.2 [M + Na]⁺.

Supplementary Material

Supporting Information