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Synlett 2013; 24(1): 69-72
DOI: 10.1055/s-0032-1317860
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 2-Thioaldoses via BF3-Promoted Cycloaddition of β-Methoxyvinyl Sulfides with 2,3-O-Isopropylidene Derivatives of aldehydo-Aldoses

Hideyuki Sugimura*
Department of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1, Fuchinobe, Chuo-ku, Sagamihara-shi 252-5258, Japan   Fax: +81(42)7596227   Email: sugimura@chem.aoyama.ac.jp
,
Kousuke Kusakabe
Department of Chemistry and Biological Science, Aoyama Gakuin University, 5-10-1, Fuchinobe, Chuo-ku, Sagamihara-shi 252-5258, Japan   Fax: +81(42)7596227   Email: sugimura@chem.aoyama.ac.jp
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Publication History

Received: 26 October 2012

Accepted after revision: 20 November 2012

Publication Date:
10 December 2012 (online)

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Abstract

A highly stereoselective approach to the synthesis of 2-thioaldose derivatives via BF3-promoted cycloaddition of β-methoxyvinyl sulfides with 2,3-O-isopropylidene derivatives of ­aldehydo-aldoses is described.

Key words

aldehydes - boron - carbohydrates - cycloaddition - sulfur

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

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  • 12 According to a literature procedure, vinyl sulfides 3a–c were prepared using BuLi instead of t-BuLi: Maddaluno J, Gaonach O, Marcual A, Toupet L, Giessner-Prettre C. J. Org. Chem. 1996; 61: 5290
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  • 13 General Procedure for the Cyclization: To a solution of aldehyde (1.0 mmol) and β-methoxyvinyl sulfide (1.5 mmol) in anhyd CH2Cl2 (10 mL) under argon atmosphere was added BF3·OEt2 (1.2 mmol) dropwise at –78 °C. After being stirred for 2–3 h at –78 °C, the reaction mixture was quenched with Et3N (0.5 mL). The resulting mixture was poured into sat. aq NaHCO3. After the phase separation, the aqueous layer was extracted twice with CH2Cl2. The organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane–EtOAc, 19:1 → 9:1) to afford the corresponding cycloadduct.
  • 14 Methyl 3,5;6,7-Di-O-isopropylidene-2-deoxy-2-phenylthio-β-d-glycero- d -ido-heptofuranoside (5a): 1H NMR (500 MHz, CDCl3): δ = 1.34 (s, 3 H), 1.37 (s, 3 H), 1.39 (s, 3 H), 1.42 (s, 3 H), 3,49 (s, 3 H), 3.88 (dd, J = 2.3, 7.8 Hz, 1 H), 3.94 (d, J = 5.5 Hz, 1 H), 3.97 (d, J = 5.0 Hz, 1 H), 4.07 (dd, J = 6.0, 8.7 Hz, 1 H), 4.22 (t, J = 2.3 Hz, 1 H), 4.27 (d, J = 2.3 Hz, 1 H), 4.31–4.36 (m, 1 H), 5.43 (d, J = 5.5 Hz, 1 H), 7.16–7.36 (m, 5 H). 13C NMR (125 MHz, CDCl3): δ = 19.5, 25.3, 26.9, 29.2, 55.4, 56.3, 66.7, 69.5, 69.7, 74.6, 77.1, 98.4, 103.5, 109.1, 125.9, 128.5, 129.0, 136.1. Methyl 3,5;6,7-Di-O-isopropylidene-2-deoxy-2-(2-naphthylthio)-β-d-glycero- d -ido-heptofuranoside (5b): 1H NMR (500 MHz, CDCl3): δ = 1.33 (s, 3 H), 1.37 (s, 3 H), 1.42 (2 × s, 6 H), 3.51 (s, 3 H), 3.89 (d, J = 7.3 Hz, 1 H), 3.96 (dd, J = 5.0, 8.7 Hz, 1 H), 4.07–4.10 (m, 2 H), 4.24 (s, 1 H), 4.33–4.37 (m, 2 H), 5.47 (d, J = 5.5 Hz, 1 H), 7.41–7.49 (m, 3 H), 7.71–7.84 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 25.3, 26.9, 29.3, 55.4, 56.3, 66.7, 69.6, 69.7, 74.6, 77.1, 98.4, 103.5, 109.1, 125.6, 125.9, 126.6, 126.7, 127.0, 127.7, 128.4, 131.5, 133.8, 133.9. Methyl 3,5;6,7-Di-O-isopropylidene-2-deoxy-2-benzylthio-β-d-glycero- d -ido-heptofuranoside (5c): 1H NMR (500 MHz, CDCl3): δ = 1.32 (s, 3 H), 1.34 (s, 3 H), 1.35 (s, 3 H), 1.40 (s, 3 H), 3.35 (d, J = 5.5 Hz, 1 H), 3.41 (s, 3 H), 3.76 (d, J = 13.0 Hz, 1 H), 3.78 (d, J = 13.0 Hz, 1 H), 3.85(dd, J = 2.3, 7.3 Hz, 1 H), 3.93 (dd, J = 5.0, 8.7 Hz, 1 H), 4.03–4.05 (m, 1 H), 4.06 (t, J = 2.3 Hz, 1 H), 4.11 (d, J = 2.3 Hz, 1 H), 4.28 (dd, J = 5.0, 6.0, 7.3 Hz, 1 H), 5.21 (d, J = 5.5 Hz, 1 H), 7.22–7.33 (m, 5 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 25.3, 26.9, 29.2, 37.1, 54.5, 56.1, 66.7, 69.4, 69.6, 74.6, 77.2, 98.1, 103.7, 109.0, 127.1, 128.5, 129.1, 137.9.
  • 15 Methyl 6-O-tert-Butyldimethylsilyl-3,5-O-isopropylidene-2-deoxy-2-benzylthio-α-d-glucofuranoside (7a): 1H NMR (500 MHz, CDCl3): δ = 0.08 (s, 6 H), 0.91 (s, 9 H), 1.35 (s, 3 H), 1.38 (s, 3 H), 3.20 (t, J = 4.6 Hz, 1 H), 3.31 (s, 3 H), 3.61 (ddd, J = 2.8, 6.0, 9.2 Hz, 1 H), 3.73 (dd, J = 6.0, 11.0 Hz, 1 H), 3.80–3.85 (m, 3 H), 4.09 (dd, J = 5.5, 8.7 Hz, 1 H), 4.36 (dd, J = 5.0, 5.5 Hz, 1 H), 4.80 (d, J = 5.0 Hz, 1 H), 7.23–7.38 (m, 5 H). 13C NMR (125 MHz, CDCl3): δ = –5.3, –5.2, 18.4, 24.0, 25.2, 25.8, 36.1, 52.4, 55.2, 63.6, 71.6, 75.5, 78.8, 100.5, 103.5, 127.0, 128.4, 129.1, 138.3. Methyl 6-O-tert-Butyldiphenylsilyl-3,5-O-isopropylidene-2-deoxy-2-benzylthio-α-d-glucofuranoside (7b): 1H NMR (500 MHz, CDCl3): δ = 1.04 (s, 9 H), 1.35 (s, 3 H), 1.38 (s, 3 H), 3.19 (t, J = 4.6, 1 H), 3.27 (s, 3 H), 3.69 (ddd, J = 2.8, 6.0, 9.2 Hz, 1 H), 3.76–3.84 (m, 3 H), 3.86 (dd, J = 2.8, 11.0 Hz, 1 H), 4.13 (dd, J = 5.5, 8.7 Hz, 1 H), 4.35 (dd, J = 5.0, 5.5 Hz, 1 H), 4.77 (d, J = 5.0 Hz, 1 H), 7.22–7.42 (m, 11 H), 7.69–7.71 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 19.3, 24.1, 25.2, 26.7, 36.1, 52.4, 55.2, 64.4, 71.6, 75.6, 78.8, 100.4, 103.5, 127.0, 127.5, 127.5, 128.4, 129.1, 129.5, 133.6, 133.7, 135.6, 135.7, 138.3.
  • 16 Methyl 3,4,6-Tri-O-acetyl-2-deoxy-2-benzylthio-α,β-d-glucopyranoside (8): 1H NMR (500 MHz, CDCl3; assigned to the α-anomer): δ = 2.03 (s, 3 H), 2.07 (s, 3 H), 2.08 (s, 3 H), 2.80 (dd, J = 3.2, 11.5 Hz, 1 H), 3.35 (s, 3 H), 3.75 (d, J = 13.3 Hz, 1 H), 3.81 (dd, J = 13.3 Hz, 1 H), 3.98 (ddd, J = 2.3, 4.6, 10.1 Hz, 1 H), 4.04 (dd, J = 2.3, 12.4 Hz, 1 H), 4.28 (dd, J = 4.6, 12.4 Hz, 1 H), 4.64 (d, J = 3.2 Hz, 1 H), 4.96 (dd, J = 9.2, 10.1 Hz, 1 H), 5.44 (dd, J = 9.2, 11.5 Hz, 1 H), 7.23–7.33 (m, 5 H). 13C NMR (125 MHz, CDCl3): δ = 20.6, 20.6, 20.7, 20.8, 36.3, 36.8, 48.3, 49.1, 55.5, 57.5, 62.1, 62.1, 67.4, 69.4, 69.7, 71.4, 71.5, 72.3, 100.7, 106.0, 127.1, 127.3, 128.4, 128.6, 128.9, 129.1, 137.8, 169.8, 170.0, 170.6.