Synthesis of Spirolactonic C-Sialosides Induced by Samarium Diiodide

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-3_eq), 2.17, 2.10, 2.07 (s, 3 × 3 H, 3OAc), 2.05 (m, 1 H, H-3_ax), 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-3_eq, CH₂), 2.74–2.64 (m, 1 H, CH₂), 2.17, 2.12 (s, 2 × 3 H, 2OAc) 2.07 (m, 1 H, H-3_ax), 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-3_eq), 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-3_eq), 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-3_ax), 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).
• 28 The X-ray diffraction data were collected with a Kappa X8 APPEX II Bruker diffractometer with graphite-monochromated Mo_Kα radiation (λ = 0.71073 Å). CCDC 959507 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/Community/Requestastructure.

For the formation of similar spirocyclic six-membered lactones by using a SmI₂-mediated aldol reaction with aldehydes, see:
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