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Synlett 2009(18): 2957-2960  
DOI: 10.1055/s-0029-1218272
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Intramolecular Glycosylation Approach toward Constructing the Macrocyclic Structure of Resin Glycosides

Sang-Hyun Sona, Natsuko Yanagiyaa, Jun-ichi Furukawab, Nobuo Sakairi*a
a Graduate School of Environmental Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan
Fax: +81(11)7062257; e-Mail: nsaka@ees.hokudai.ac.jp;
b Graduate School of Advanced Life Science, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan
Further Information

Publication History

Received 26 August 2009
Publication Date:
08 October 2009 (online)

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Abstract

Oligosaccharide-containing macrolides of resin glycosides were effectively constructed by MeOTf-promoted intramolecular glycosylation of dodecyl thioglycosyl donors. Synthesis of a key disaccharide intermediate of tricolorin A and total synthesis of tricolorin F were successfully achieved by this approach.

Key words

resin glycoside - macrolide - tricolorin - dodecyl thioglycoside - intramolecular glycosylation

    References and Notes

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14

All new compounds had satisfactory data for elemental analysis or high resolution mass spectrum.
Selected Physical Data
Compound (R,S)-5: ¹H NMR (300 MHz, CDCl3): δ = 8.02-7.25 (m, 20 H, CHarom), 5.45 (t, 1 H, J 3 ′ ,4 ′ = 9.4 Hz, H-3′), 5.19 (t, 1 H, J 2 ′ ,3 ′ = 9.8 Hz, H-2′), 4.97-4.61 (m, 6 H, PhCH2), 4.57 (d, 1 H, J 1 ′ ,2 ′ = 10.0 Hz, H-1′), 4.25 (d, 1 H, J 1,2 = 7.1 Hz, H-1), 3.61-3.48 (m, 4 H, H-2, H-3, H-5′, OCH), 3.41-3.33 (m, 2 H, H-5, H-4′), 3.20 (t, 1 H, J 4,5 = 8.6 Hz, H-4), 2.69-2.63 (m, 2 H, SCH2), 2.26 (s, 1 H, OH), 2.09 (t, 2 H, J = 7.3 Hz, CH2COO), 1.57-0.85 (m, 56 H, H-6, H-6′, 22 × CH2, 2 × CH3). Although (R)-5 and (S)-5 were not distinguished by both ¹H NMR and ¹³C NMR spectra, the diastereomeric ratio of almost 1:1 was deduced by careful HPTLC (Merck) analysis on silica gel using hexane-EtOAc (2:1).
Compound (R)-6: [α]D +13.3 (c 1.05, CHCl3). ¹H NMR (300 MHz, CDCl3): δ = 7.90-7.19 (m, 20 H, CHarom), 5.41 (t, 1 H, J 3 ′ ,4 ′ = 8.6 Hz, H-3′), 5.23 (t, 1 H, J 2 ′ , 3 ′ = 7.7 Hz, H-2′), 5.14 (d, 1 H, J 1 ′ ,2 ′ = 7.7 Hz, H-1′), 4.75-4.48 (m, 6 H, PhCH2), 4.39 (d, 1 H, J 1,2 = 7.7 Hz, H-1), 3.85-3.76 (m, 2 H, H-2, OCH), 3.53-3.45 (m, 1 H, H-5′), 3.42 (t, 1 H, J 4 ′ ,5 ′ = 9.2 Hz, H-4′), 3.41 (t, 1 H, J 3,4 = 8.5 Hz, H-3), 3.29-3.22 (m, 1 H, H-5), 3.11 (t, 1 H, J 4,5 = 9.1 Hz, H-4), 2.29-2.08 (m, 2 H, CH2COO), 1.67-1.21 (m, 30 H, H-6, H-6′, 12 × CH2), 0.88 (t, 3 H, J = 6.7 Hz, CH2CH 3). ¹³C NMR (75.5 MHz, CDCl3): δ = 172.4, 165.4, 138.5, 138.1, 133.4, 130.2, 130.1, 129.0, 128.8, 128.4, 128.4, 128.2, 128.0, 99.6, 95.6, 86.4, 84.4, 82.9, 81.0, 76.2, 75.8, 75.6, 75.4, 74.9, 71.2, 71.1, 34.9, 34.5, 34.5, 32.6, 31.2, 29.4, 28.3, 28.0, 27.9, 26.9, 23.1, 18.5, 18.4, 14.6. HRMS-FAB: m/z calcd for C56H72O11 [M + Na]+: 943.4995; found: 943.4995.
Compound (S)-6: [α]D +25.6 (c 0.20, CHCl3). ¹H NMR (300 MHz, CDCl3): δ = 7.92-7.17 (m, 20 H, CHarom), 5.42 (t, 1 H, J 3 ′ ,4 ′ = 8.6 Hz, H-3′), 5.23 (t, 1 H, J 2 ′ ,3 ′ = 8.3 Hz, H-2′), 5.07 (d, 1 H, J 1 ′ ,2 ′ = 7.6 Hz, H-1′), 4.75-4.46 (m, 6 H, PhCH2), 4.24 (d, 1 H, J 1,2 = 7.8 Hz, H-1), 3.82 (dd, 1 H, J = 8.0 Hz, J 2,3 = 9.3 Hz, H-2), 3.53-3.46 (m, 2 H, H-5′, OCH), 3.40 (t, 1 H, J 4 ′ ,5 ′ = 9.2 Hz, H-4′), 3.40 (t, 1 H, J 3,4 = 8.4 Hz, H-3), 3.31-3.26 (m, 1 H, H-5), 3.11 (t, 1 H, J 4,5 = 9.2 Hz, H-4), 2.19 (s, 2 H, CH2COO), 1.59-1.22 (m, 30 H, H-6, H-6′, 12 × CH2), 0.89 (t, 3 H, J 1,2 = 6.4 Hz, CH2CH 3). ¹³C NMR (75.5 MHz, CDCl3): δ = 172.4, 165.5, 138.5, 138.2, 133.4, 130.2, 130.1, 129.0, 128.9, 128.8, 128.4, 128.3, 128.3, 128.2, 128.0, 102.3, 99.5, 86.1, 84.1, 83.2, 82.2, 76.5, 75.8, 75.6, 75.5, 75.1, 71.5, 70.9, 35.3, 35.0, 34.6, 32.5, 31.6, 29.8, 28.4, 28.1, 27.3, 25.7, 25.4, 23.4, 23.1, 18.4, 14.6. HRMS-FAB: m/z calcd for C56H72O11 [M + Na]+: 943.4995; found: 943.4995.
Compound 12: [α]D -7.2 (c 0.76, CHCl3). ¹H NMR (300 MHz, acetone-d 6): δ = 7.40-7.25 (m, 10 H, 2 CHarom), 5.40 (t, 1 H, J 3 ′ ,4 ′ = 8.9 Hz, H-3′), 4.97-4.57 (m, 6 H, PhCH2, Cl3CCH2), 4.82 (d, 1 H, J 1 ′ ,2 ′ = 10.0 Hz, H-1′), 4.73 (t, 1 H, J 2 ′ ,3 ′ = 9.6 Hz, H-2′), 4.22 (d, 1 H, J 1,2 = 8.1 Hz, H-1), 4.03 (dd, 1 H, J = 2.2 Hz, J 4,5 = 6.0 Hz, H-4), 4.00-3.96 (m, 1 H, H-3), 3.91 (dd, 1 H, J = 2.1, 6.5 Hz, H-5), 3.86-3.75 (m, 4 H, H-4′, H-5′, H-6′a, H-6′b), 3.63-3.60 (m, 1 H, CHO), 3.35 (t, 1 H, J 2,3 = 7.6 Hz, H-2), 2.85-2.65 (m, 2 H, SCH2), 2.33-2.20 (m, 2 H, CH2COO), 1.52-1.28 [m, 53 H, H-6, C(CH3)2, 22 × CH2], 0.91-0.86 (m, 6 H, 2 × CH3). Column chromatography of the mixture gave crude 12 contaminated with small amount of an unknown product in ca. 60% yield and a mixture of 11 its 3-O-Troc derivative. Repeated column chromatography gave pure 12 in 12% yield.
Compound 13: [α]D +2.1 (c 0.33, CHCl3). ¹H NMR (300 MHz, acetone-d 6): δ = 7.44-7.29 (m, 10 H, CHarom), 5.48 (t, 1 H, J 3 ′ ,4 ′ = 8.6 Hz, H-3′), 5.36 (d, 1 H, J 1 ′ ,2 ′ = 7.6 Hz, H-1′), 5.08-4.63 (m, 6 H, PhCH2, Cl3CCH2), 4.57 (dd, 1 H, J = 7.6 Hz, J 2 ′ ,3 ′ = 8.8 Hz, H-2′), 4.23 (d, 1 H, J 1,2 = 8.4 Hz, H-1), 4.11 (dd, 1 H, J = 5.3 Hz, J 4,5 = 7.0 Hz, H-4), 4.05 (dd, 1 H, J = 2.0 Hz, J 3,4 = 5.3 Hz, H-3), 3.95-3.84 (m, 5 H, H-2, H-5, H-4′, H-6′a, H-6′b), 3.71-3.65 (m, 1 H, H-5′), 3.55-3.49 (m, 1 H, CHO), 2.33-2.00 (m, 2 H, CH2COO), 1.53-1.24 [m, 33 H, H-6, C(CH3)2, 12 × CH2], 0.86 (t, 3 H, J = 6.8 Hz, CH2CH 3). ¹³C NMR (75.5 MHz, acetone-d 6): δ = 171.8, 153.4, 139.1, 138.8, 128.6, 128.3, 128.2, 128.0, 127.7, 109.6, 101.5, 97.0, 95.3, 81.2, 80.5, 80.2, 77.0, 76.9, 75.5, 75.1, 74.7, 74.5, 73.5, 68.6, 68.3, 35.4, 35.2, 34.5, 32.1, 31.1, 30.1, 29.9, 29.6, 29.3, 29.1, 28.8, 28.6, 28.3, 28.2, 27.9, 27.4, 26.3, 25.4, 25.1, 24.2, 22.8, 16.7, 13.9. HRMS-FAB: m/z calcd for C48H67Cl3O13 [M + Na]+: 979.3545; found: 979.3542.
Compound 19: [α]D -20.5 (c 0.064, CHCl3). ¹H NMR (600 MHz, acetone-d 6): δ = 7.41-7.20 (m, 25 H, CHarom), 5.06 (d, 1 H, J 1 ′ , 2 ′ = 7.4 Hz, H-1′), 5.01 (s, 1 H, H-1′′), 5.01 (t, 1 H, J 2 ′′ ,3 ′′ = 4.5 Hz, H-2′′), 5.01-4.61 (m, 10 H, PhCH2), 4.45 (t, 1 H, J 3,4 = 6.3 Hz, H-3), 4.42 (d, 1 H, J 1,2 = 6.4 Hz, H-1), 4.12 (dd, 1 H, J = 2.0 Hz, J 4,5 = 5.7 Hz, H-4), 3.98-3.91 (m, 1 H, H-5), 3.94 (t, 1 H, J 2,3 = 6.4 Hz, H-2), 3.80-3.74 (m, 2 H, H-6′a, 6′b), 3.69 (t, 1 H, J 3 ′ ,4 ′ = 7.7 Hz, H-3′), 3.64 (m, 1 H, H-3′′), 3.61 (t, 1 H, J 2 ′ ,3 ′ = 7.4 Hz, H-2′), 3.58 (t, 1 H, J 4 ′ ,5 ′ = 7.3 Hz, H-4′), 3.56 (m, 2 H, H-5′′, CHO), 3.46-3.42 (m, 1 H, H-5′), 3.32 (t, 1 H, J 4 ′′ , 5 ′′ = 9.1 Hz, H-4′′), 2.13 (t, 2 H, J = 7.6 Hz, CH2COO), 1.70-0.85 [m, 39 H, H-6, H-6′′, 12 × CH 2, C(CH3)2, CH2CH 3]. ¹³C NMR (75.5 MHz, acetone-d 6): δ = 172.6, 138.9, 138.7, 138.5, 138.3, 129.0, 128.9, 128.8, 128.6, 128.5, 128.3, 128.2, 128.1, 127.9, 127.6, 110.2, 102.9, 100.8, 83.8, 78.7, 77.7, 75.9, 75.8, 75.6, 75.5, 75.4, 74.0, 72.0, 68.8, 36.6, 35.4, 34.5, 32.5, 30.2, 30.1, 29.4, 28.2, 28.1, 28.0, 26.9, 25.5, 23.1, 18.7, 17.3, 14.6. HRMS-FAB: m/z calcd for C72H96O15 [M + H]+: 1199.6672; found: 1199.6640.