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Synlett 2014; 25(3): 375-380
DOI: 10.1055/s-0033-1340067
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Spirolactonic C-Sialosides Induced by Samarium Diiodide

Justine Pezzotta
a   Laboratoire de Synthèse de Biomolécules, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), Université Paris-Sud and CNRS, 91405 Orsay, France
,
Dominique Urban
a   Laboratoire de Synthèse de Biomolécules, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), Université Paris-Sud and CNRS, 91405 Orsay, France
,
Régis Guillot
b   Service de Cristallographie, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), Université Paris-Sud and CNRS, 91405 Orsay, France   Fax: +33(1)69853715   Email: gilles.doisneau@u-psud.fr   Email: jean-marie.beau@u-psud.fr
,
Gilles Doisneau*
a   Laboratoire de Synthèse de Biomolécules, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), Université Paris-Sud and CNRS, 91405 Orsay, France
,
Jean-Marie Beau*
a   Laboratoire de Synthèse de Biomolécules, Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), Université Paris-Sud and CNRS, 91405 Orsay, France
c   Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles du CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France   Email: jean-marie.beau@cnrs.fr
› Author Affiliations
Further Information

Publication History

Received: 18 September 2013

Accepted after revision: 01 October 2013

Publication Date:
05 November 2013 (online)

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Abstract

A method for the synthesis of spiro-δ-lactonic α-C-sialosides by samarium diiodide mediated cyclization reactions of glycosyl 2-pyridylsulfides or acetates with appropriate carbonyl side chains has been developed.

Key words

carbohydrates - chemoselectivity - coupling - cyclization - samarium
 

  • References and Notes

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  • 19 Selected Spectroscopic Data; Acid 2: 1H NMR (CDCl3, 360 MHz): δ = 8.78 (d, J = 5.2 Hz, 1 H, ArH), 7.81 (t, J = 7.7 Hz, 1 H, ArH), 7.40 (d, J = 7.7 Hz, 1 H, ArH), 7.31 (dd, J = 7.7, 5.2 Hz, 1 H, ArH), 6.59 (d, J NH–H5 = 10.1 Hz, 1 H, NH), 5.37 (ddd, J H4–H3ax = 10.8 Hz, J H4–H5 = 10.1 Hz, J H4–H3eq = 5.4 Hz, 1 H, H-4), 5.34 (dd, J H7–H8 = 8.1 Hz, J H7–H6 = 1.8 Hz, 1 H, H-7), 5.08 (ddd, J H8–H7 = 8.1 Hz, J H8–H9b = 5.5 Hz, J H8–H9a = 2.8 Hz, 1 H, H-8), 4.19 (q, J H5–H6 = J H5–H4 = J H5–NH = 10.1 Hz, 1 H, H-5), 4.09 (dd, J H9a–H9b = 12.2 Hz, J H9a–H8 = 2.8 Hz, 1 H, H-9a), 4.04 (dd, J H6–H5 = 10.1 Hz, J H6–H7 = 1.8 Hz, 1 H, H-6), 3.89 (dd, J H9b–H9a = 12.2 Hz, J H9b–H8 = 5.5 Hz, 1 H, H-9b), 2.88 (dd, J H3eq–H3ax = 12.3 Hz, J H3eq–H4 = 5.4 Hz, 1 H, H-3eq), 2.17, 2.10, 2.07 (s, 3 × 3 H, 3OAc), 2.05 (m, 1 H, H-3ax), 2.04 (s, 3 H, OAc), 1.94 (s, 3 H, NHAc). 13C NMR (CDCl3, 90 MHz): δ = 170.9, 170.6, 170.5, 170.4, 169.9, 169.7 (6C, 6CO), 153.7, 147.3, 139.3, 124.6, 121.8 (5C, 5C-Ar), 85.7 (C-2), 74.8 (C-6), 69.9 (C-4), 68.8 (C-8), 66.8 (C-7), 61.6 (C-9), 49.3 (C-5), 37.8 (C-3), 23.1 (NHAc), 20.7–21.0 (4C, 4OAc). HRMS: m/z calcd for C24H30N2NaO12S: 593.1417; found: 593.1405. Pyridylsulfide 18: 1H NMR (CDCl3, 400 MHz): δ = 8.46 (ddd, J = 4.8, 1.8, 0.9 Hz, 1 H, ArH), 7.67 (dt, J = 7.8, 1.8 Hz, 1 H, ArH), 7.58 (dt, J = 7.8, 0.9 Hz, 1 H, ArH), 7.19 (ddd, J = 7.8, 4.8, 0.9 Hz, 1 H, ArH), 5.56 (d, J NH–H5 = 9.2 Hz, 1 H, NH), 5.32 (dd, J H7–H8 = 8.0 Hz, J H7–H6 = 1.2 Hz, 1 H, H-7), 5.21 (ddd, J H8–H7 = 8.0 Hz, J H8–H9b = 5.2 Hz, J H8–H9a = 2.7 Hz, 1 H, H-8), 4.85 (ddd, J H4–H3ax or H5 = 11.4 Hz, J H4–H5 or H3ax = 10.1 Hz, J H4–H3eq = 4.7 Hz, 1 H, H-4), 4.56–4.50 (m, 1 H, CH2-O), 4.29 (dd, J H9a–H9b = 12.4 Hz, J H9a–H8 = 2.7 Hz, 1 H, H-9a), 4.20–4.05 (m, 4 H, H-9b, H-6, H-5, CH2-O), 2.90-2.80 (m, 2 H, H-3eq, CH2), 2.74–2.64 (m, 1 H, CH2), 2.17, 2.12 (s, 2 × 3 H, 2OAc) 2.07 (m, 1 H, H-3ax), 2.05, 2.02 (s, 2 × 3 H, 2OAc), 2.01 (s, 3 H, Me), 1.98 (s, 3 H, NHAc). 13C NMR (CDCl3, 100 MHz): δ = 206.1 (ketone), 170.6, 170.2, 170.0, 167.3 (6C, 6CO), 153.1, 149.7, 137.2, 129.1, 122.8 (5C, 5C-Ar), 86.0 (C-2), 74.6 (C-6), 69.5 (C-4), 69.4 (C-8), 67.5 (C-7), 62.0 (C-9), 60.5 (CH2), 48.8 (C-5), 41.8 (CH2), 38.3 (C-3), 30.1 (Me), 23.2 (NHAc), 20.8–21.0 (4C, 4OAc). HRMS: m/z calcd for C28H36N2NaO13S: 663.1836; found: 663.1857. Lactones 21: First eluted isomer 21R: 1H NMR (CDCl3, 400 MHz): δ = 5.75 (d, J NH–H5 = 10.0 Hz, 1 H, NH), 5.62 (ddd, J H4–H3ax = 10.7 Hz, J H4–H5 = 10.0 Hz, J H4–H3eq = 5.7 Hz, 1 H, H-4), 5.32 (dd, J H7–H8 = 9.6 Hz, J H7–H6 = 2.4 Hz, 1 H, H-7), 5.23 (ddd, J H8–H7 = 9.6 Hz, J H8–H9b = 5.5 Hz, J H8–H9a = 2.7 Hz, 1 H, H-8), 4.48 (ddd, J = 11.2, 10.7, 4.7 Hz, 1 H, CH2-O), 4.26 (ddd, J = 11.2, 6.2, 2.7 Hz, 1 H, CH2-O), 4.26 (dd, J H9a–H9b = 12.8 Hz, J H9a–H8 = 2.7 Hz, 1 H, H-9a), 4.07 (q, J H5–H6 = J H5–H4 = J H5–NH = 10.0 Hz, 1 H, H-5), 3.97 (dd, J H9b–H9a = 12.8 Hz, J H9b–H8 = 5.5 Hz, 1 H, H-9b), 3.95 (dd, J H6–H5 = 10.0 Hz, J H6–H7 = 2.4 Hz, 1 H, H-6), 2.52 (s, 1 H, OH), 2.44 (ddd, J = 14.3, 10.7, 6.2 Hz, 1 H, CH2), 2.32 (dd, J H3eq–H3ax = 13.6 Hz, J H3eq–H4 = 5.7 Hz, 1 H, H-3eq), 2.11, 2.08, 2.03, 2.01 (s, 4 × 3 H, 4OAc), 1.95 (dd, J H3ax–H3eq = 13.6 Hz, J H3ax–H4 = 10.7 Hz, 1 H, H-3ax), 1.89 (s, 3 H, NHAc), 1.68 (ddd, J = 14.3, 4.7, 2.7 Hz, 1 H, CH2), 1.42 (s, 3 H, Me). 13C NMR (CDCl3, 100 MHz): δ = 171.0, 170.7, 170.6, 170.0, 169.8 (6C, 6CO), 79.7 (C-2), 73.2 (C-OH), 72.7 (C-6), 70.8 (C-4), 68.0 (C-8), 67.0 (C-7), 66.2 (CH2), 62.3 (C-9), 49.2 (C-5), 32.0 (CH2), 30.5 (C-3), 23.5 (CH3), 23.1 (NHAc), 20.7, 20.8, 21.0 (4C, 4OAc). HRMS: m/z calcd for C23H33NNaO13: 554.1850; found: 554.1831. Second eluted isomer 21S: 1H NMR (CDCl3, 400 MHz): δ = 5.87 (d, J NH–H5 = 10.8 Hz, 1 H, NH), 5.40 (ddd, J H8–H7 = 9.6 Hz, J H8–H9b = 5.6 Hz, J H8–H9a = 2.4 Hz, 1 H, H-8), 5.34 (dd, J H7–H8 = 9.6 Hz, J H7–H6 = 2.5 Hz, 1 H, H-7), 5.21 (ddd, J H4–H3ax = 11.6 Hz, J H4–H5 = 10.8 Hz, J H4–H3eq = 4.8 Hz, 1 H, H-4), 4.73 (dd, J H6–H5 = 10.8 Hz, J H6–H7 = 2.5 Hz, 1 H, H-6), 4.56 (ddd, J = 11.3, 8.7, 6.0 Hz, 1 H, CH2-O), 4.27 (ddd, J = 11.3, 6.6, 4.5 Hz, 1 H, CH2-O), 4.23 (dd, J H9a–H9b = 12.4 Hz, J H9a,H8 = 2.4 Hz, 1 H, H-9a), 4.12 (q, J H5–H4 = J H5,H6 = J H5,NHAc = 10.8 Hz, 1 H, H-5), 4.02 (dd, J H9b–H9a = 12.4 Hz, J H9b–H8 = 5.6 Hz, 1 H, H-9b), 3.39 (s, 1 H, OH), 2.29 (dd, J H3eq–H3ax = 13.2 Hz, J H3eq–H4 = 4.8 Hz, 1 H, H-3eq), 2.15, 2.14 (s, 2 × 3 H, 2OAc), 2.09 (m, 1 H, CH2), 2.06, 2.01 (s, 2 × 3 H, 2 × OAc), 1.97 (m, 1 H, CH2), 1.94 (dd, J H3ax–H3eq = 13.2 Hz, J H3ax–H4 = 11.6 Hz, 1 H, H-3ax), 1.90 (s, 3 H, NHAc), 1.36 (s, 3 H, Me). 13C NMR (CDCl3, 100 MHz): δ = 172.7, 170.8, 170.7, 170.5, 170.4, 170.0 (6C, 6CO), 80.7 (C-2), 73.6 (C-6 or C-OH), 73.4 (C-6 or C-OH), 69.6 (C-4), 67.7 (C-8), 67.2 (C-7), 66.6 (CH2), 62.8 (C-9), 49.1 (C-5), 32.9 (C-3), 32.7 (CH2), 23.1 (NHAc), 21.7 (CH3), 20.7, 20.8, 20.9, 21.0 (4C, 4OAc). HRMS: m/z calcd for C23H33NNaO13: 554.1850; found: 554.1831.
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  • 27 Reductive Cyclization of 18; Typical Procedure: A freshly prepared solution of samarium diiodide (0.1m in THF, 4.7 mL, 3.0 equiv) was added to sialyl derivative 18 (100 mg, 0.16 mmol) previously dissolved in THF (0.5 mL) under an argon atmosphere. The solution was stirred at r.t. for 2 h. The initial blue color of the mixture then became yellow. The reaction was quenched by the addition of a few drops of a sat. aq NH4Cl. The aqueous layer was extracted four times with CH2Cl2 and the organics layers were combined and washed with sat. aq NaHCO3. The aqueous layers were extracted three times with CH2Cl2 and the organic layers were combined, dried under Na2SO4, filtered and concentrated under vacuum. The obtained residue was purified by silica gel chromatography (toluene–acetone, 3:1 to 2:1), furnishing the separated two stereoisomers of spirolactones 21 (75 mg total, 0.14 mmol, 90%). Spirolactone 21S was recrystallized in CH2Cl2/Et2O (mp 207 °C).
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