Benzenesulfinyl Morpholine: A New Promoter for One-Pot Oligosaccharide Synthesis Using Thioglycosides by Pre-Activation Strategy

Changning Wang; Haisheng Wang; Xuefei Huang; Li-He Zhang; Xin-Shan Ye

doi:10.1055/s-2006-950247

LETTER

Benzenesulfinyl Morpholine: A New Promoter for One-Pot Oligosaccharide Synthesis Using Thioglycosides by Pre-Activation Strategy

Changning Wang^a, Haisheng Wang^a, Xuefei Huang^b, Li-He Zhang^a, Xin-Shan Ye*^a
^a The State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd 38, Beijing 100083, P. R. of China
Fax: +86(10)62014949; e-Mail: xinshan@bjmu.edu.cn;
^b Department of Chemistry, University of Toledo, 2801 W. Bancroft Street, MS 602, Toledo, OH 43606, USA

Abstract

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Abstract

Benzenesulfinyl morpholine (BSM) has been applied as a new promoter for the activation of thioglycosides. This proceeds by the in situ reaction of BSM with trifluoromethanesulfonic anhydride, which subsequently activates thioglycosides for glycosylations. Importantly, this reagent works well in our pre-activation one-pot oligosaccharide assembly strategy.

Key words

benzenesulfinyl morpholine - promoter - thioglycoside - pre-activation - one-pot oligosaccharide assembly

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References

References and Notes

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17

Other compounds such as methyl phenyl sulfoxide, 2-(phenylthio)quinoline, 2-(phenylthio)thiophene, N-phenylsulfanyl phthalimide, N-benzenesulfenyl succinimide were examined, but all these compounds did not give better results than BSM.

For the preparation of BSM, see:

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21

General Procedure for Oligosaccharide Assembly.
To a solution of 1 (100.0 mg, 0.155 mmol), and BSM (49.1 mg, 0.233 mmol) in CH₂Cl₂ (4 mL) was added 4 Å MS (40 mg), and the mixture was cooled down to -70 °C, and then Tf₂O (26.2 mg, 0.093 mmol) was added, after 5 min, 1 was consumed completely. After addition of the acceptor 2 (66.7 mg, 0.140 mmol) to the preactivated donor, the mixture was stirred for 15 min. Then the reaction mixture was warmed up to r.t. for 15 min. The mixture was cooled down to -70 °C again, Tf₂O (43.7 mg, 0.155 mmol) was added, after 5 min, and the new formed disaccharide was consumed completely. After addition of the acceptor 11 (71.9 mg, 0.155 mmol) to the preactivated donor, the mixture was stirred for 15 min. Then the reaction mixture was warmed up to r.t. for 15 min. The course of the reaction was monitored by TLC. Then, Et₃N (0.5 mL) was then added to the mixture. The precipitate was filtered off and the filtrate was concentrated. The residue was purified by column chromatography on silica gel to give 12 (126.9 mg, 52%). ¹H NMR (500 MHz, CDCl₃): δ = 2.97 (s, 1 H), 3.16 (dd, 1 H, J = 6.0, 9.0 Hz), 3.22-3.28 (m, 2 H), 3.39 (t, 1 H, J = 7.5 Hz), 3.46-3.48 (m, 5 H), 3.60-3.68 (m, 4 H), 3.73 (d, 1 H, J = 11.0 Hz), 3.79 (dd, 1 H, J = 3.5, 10.0 Hz), 3.84 (t, 1 H, J = 6.5 Hz), 3.88-3.91 (m, 1 H), 3.94-3.97 (m, 1 H), 4.11-4.26 (m, 6 H), 4.35 (t, 2 H, J = 12.0 Hz), 4.42-4.53 (m, 4 H), 4.58-4.63 (m, 2 H), 4.69 (d, 1 H, J = 6.0 Hz), 4.77-4.86 (m, 4 H), 5.04 (d, 1 H, J = 3.5 Hz, H-1′′), 5.10 (d, 1 H, J = 11.0 Hz), 5.32 (s, 1 H), 5.61 (dd, 1 H, J = 8.5, 10.0 Hz), 7.06-7.38 (m, 40 H), 7.48-7.50 (m, 3 H), 7.97-7.99 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 56.95, 66.60, 68.36, 68.73, 68.80, 69.84, 71.37, 72.13, 72.26, 73.09, 73.14, 73.22, 74.41, 74.64, 74.68, 74.92, 75.26, 75.48, 75.84, 77.64, 78.58, 81.96, 83.03, 95.55, 100.95, 101.20, 104.48, 126.39, 127.09, 127.29, 127.37, 127.45, 127.49, 127.58, 127.65, 127.81, 127.91, 127.99, 128.09, 128.15, 128.23, 128.34, 128.41, 128.70, 129.76, 129.85, 133.01, 137.77, 138.16, 138.46, 138.60, 138.65, 138.78, 139.07, 164.69. HRMS (ESI): m/z calcd for C₈₂H₈₈NO₁₇ [M + NH₄]⁺: 1358.6047; found: 1358.6053.

22

Preparation of Trisaccharide 13.
To a solution of compound 12 (80.0 mg, 0.060 mmol) in MeOH (10 mL) was added MeONa/MeOH (30 wt%, 0.4 mL), and the reaction mixture was stirred for 8 h at r.t. The mixture was neutralized (H⁺ resin, weak acid), filtered and concentrated. The resulting residue was dissolved in THF-AcOH-H₂O (2:2:1, 10 mL) and then Pd/C (10.0 mg) was added. The reaction mixture was stirred under 1 atm of H₂ for 24 h. The Pd/C was filtered off and the filtrate was concentrated. The product was purified by C-18 reverse-phase column chromatography to give 13 (28.0 mg, 90%). ¹H NMR (500 MHz, D₂O): δ = 3.29-3.30 (m, 1 H), 3.58 (s, 3 H), 3.61-3.63 (m, 1 H), 3.65-3.68 (m, 3 H), 3.71-3.87 (m, 8 H), 3.94-4.02 (m, 3 H), 4.18-4.21 (m, 2 H), 4.41 (d, 1 H, J = 8.0 Hz, H-1), 4.52 (d, 1 H, J = 7.5 Hz, H-1′), 5.14 (d, 1 H, J = 4.0 Hz, H-1′′). ¹³C NMR (125 MHz, D₂O): δ = 57.98, 60.88, 61.68, 61.74, 65.56, 68.95, 69.89, 70.03, 70.33, 71.59, 73.52, 75.21, 75.49, 75.80, 77.96, 79.38, 96.19, 103.60, 103.83. HRMS (ESI): m/z calcd for C₁₉H₃₄O₁₆Na [M + Na]⁺: 541.1739; found: 541.1748.

23 Debelder AN. Adv. Carbohydr.Chem. 1965, 20: 219

24

Data for Compound 16. ¹H NMR (500 MHz, CDCl₃): δ = 1.28 (s, 3 H), 1.31 (s, 3 H), 1.43 (s, 3 H), 1.47 (s, 3 H), 3.20-3.24 (m, 2 H), 3.32-3.40 (m, 3 H), 3.47-3.53 (m, 3 H), 3.64 (dd, 1 H, J = 7.5, 10.0 Hz), 3.69 (dd, 1 H, J = 3.0, 10.0 Hz), 3.82-3.89 (m, 2 H), 3.95-4.04 (m, 5 H), 4.12 (d, 1 H, J = 7.5 Hz), 4.18 (d, 1 H, J = 9.0 Hz), 4.22-4.30 (m, 5 H), 4.33 (d, 1 H, J = 10.5 Hz, H-1′), 4.36 (d, 1 H, J = 11.5 Hz), 4.42-4.58 (m, 7 H), 4.62 (d, 1 H, J = 11.0 Hz, H-1′′), 4.67 (t, J = 11.5 Hz, 2 H), 4.78 (d, 1 H, J = 11.0 Hz), 4.86 (d, 1 H, J = 11.5 Hz), 5.00 (d, 1 H, J = 11.0 Hz), 5.09 (d, 1 H, J = 4.0 Hz, H-1′′′), 5.39 (s, 1 H), 5.53 (d, 1 H, J = 5.0 Hz, H-1), 5.73 (dd, 1 H, J = 8.5, 10.0 Hz), 7.09-7.31 (m, 38 H, ArH), 7.36-7.41 (m, 3 H), 7.52 (d, 2 H, J = 8.0 Hz), 7.97 (d, 2 H, J = 8.0 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 24.47, 25.02, 26.01, 26.03, 66.40, 66.68, 67.29, 68.80, 69.04, 69.69, 69.84, 70.07, 70.48, 70.74, 71.35, 72.08, 72.19, 73.16, 73.26, 74.26, 74.61, 74.69, 74.94, 75.02, 75.31, 75.86, 78.56, 81.40, 84.38, 95.23, 96.33, 100.99 (2 C), 104.30, 108.51, 109.28, 126.39, 127.18, 127.26, 127.33, 127.36, 127.42, 127.47, 127.55, 127.71, 127.80, 127.98, 128.07, 128.10, 128.13, 128.19, 128.21, 128.26, 128.29, 128.61, 128.81, 129.86, 129.99, 132.72, 137.65, 138.23, 138.60, 138.68, 138.77, 138.81, 164.74. HRMS (ESI): m/z calcd for C₉₃H₁₀₄NO₂₂ [M + NH₄]⁺: 1586.7045; found: 1586.7039.