A Stereocontrolled Access to α-C-(1→3)-Linked Disaccharides Containing 2-Deoxyhexopyranoses

Petr Štěpánek; Ladislav Kniežo; Hana Dvořáková; Pavel Vojtíšek

doi:10.1055/s-2003-39288

LETTER

A Stereocontrolled Access to α-C-(1→3)-Linked Disaccharides Containing 2-Deoxyhexopyranoses

Petr Štěpánek^a, Ladislav Kniežo*^a, Hana Dvořáková^b, Pavel Vojtíšek^c
^a Department of Chemistry of Natural Compounds, Institute of Chemical Technology, Technická 5, 166 28 Prague 6, Czech Republic
Fax: +420(2)33339990; e-Mail: ladislav.kniezo@vscht.cz ;
^b NMR Laboratory, Institute of Chemical Technology, Technická 5, 166 28 Prague 6, Czech Republic
^c Department of Inorganic Chemistry, Charles University, 128 40 Prague 2, Czech Republic

Abstract

Alle Artikel dieser Rubrik

Abstract

A protected α-d-glucopyranosylacetaldehyde was converted by Wittig reaction with (thiazol-2-yl)carbonylmethylenetriphenyl phosphorane into the corresponding substituted 1-oxa-1,3-butadiene which by hetero-Diels-Alder reaction with ethyl vinyl ether afforded a mixture of two diastereoisomeric dihydropyran derivatives. These were separated by chromatography and the thiazol ring was transformed into an aldehyde group. Subsequent hydroboration afforded α-C-(1→3)-linked disaccharides containing 2-deoxyhexopyranoses of d- or l-configuration.

Key words

C-disaccharides - C-glycosides - hetero-Diels-Alder reaction - oxabutadienes - Wittig reaction

Volltext

Referenzen

References

<A NAME="RD05103ST-1">1</A> Mikros E. Labrinidis G. Pérez S. J. Carbohydr. Chem. 2000, 19: 1319

<A NAME="RD05103ST-2A">2a</A> Levy DE. Tang C. In The Chemistry of C-Glycosides, Tetrahedron Organic Chemistry Series Baldwin JE. Magnus PD. Pergamon-Elsevier Science; Oxford: 1995.

<A NAME="RD05103ST-2B">2b</A> Postema MHD. In C-Glycoside Synthesis CRC; Boca Raton/ FL: 1995.

<A NAME="RD05103ST-2C">2c</A> Vogel P. Ferrito R. Kraehenbuehl K. Baudat A. In Carbohydrate Mimics, Concept and Methods Chapleur Y. Wiley-VCH; Weinheim: 1998. p.19-48

<A NAME="RD05103ST-2D">2d</A> Du Y. Linhardt RJ. Vlahov IR. Tetrahedron 1998, 54: 9913

<A NAME="RD05103ST-2E">2e</A> Vogel P. Chimia 2001, 55: 359

<A NAME="RD05103ST-3A">3a</A> Wei A. Haudrechy A. Audin C. Jun H.-S. Haudrechy-Bretel N. Kishi Y. J. Org. Chem. 1995, 60: 2160

<A NAME="RD05103ST-3B">3b</A> Kobertz WR. Bertozzi CR. Bednarski MD. J. Org. Chem. 1996, 61: 1894

<A NAME="RD05103ST-3C">3c</A> Streicher H. Geyer A. Schmidt RR. Chem. Eur. J. 1996, 2: 502

<A NAME="RD05103ST-3D">3d</A> Witczak ZJ. Chabra R. Chojnacki J. Tetrahedron Lett. 1997, 38: 2215

<A NAME="RD05103ST-3E">3e</A> Rubinstenn G. Esnault J. Mallet J.-M. Sinaӱ P. Tetrahedron: Asymmetry 1997, 8: 1327

<A NAME="RD05103ST-3F">3f</A> Angelaud R. Landais Y. Parra-Rapado L. Tetrahedron Lett. 1997, 38: 8845

<A NAME="RD05103ST-3G">3g</A> Bornaghi L. Utille JP. Mekai ED. Mallet J.-M. Sinaӱ P. Driguez H. Carbohydr. Res. 1997, 305: 561

<A NAME="RD05103ST-3H">3h</A> Dondoni A. Zuurmond H. Boscarato A. J. Org. Chem. 1997, 62: 8114

<A NAME="RD05103ST-3I">3i</A> Sutherlin DP. Armstrong RW. J. Org. Chem. 1997, 62: 5267

<A NAME="RD05103ST-3J">3j</A> Lubineau A. Grand E. Scherrmann M.-C. Carbohydr. Res. 1997, 297: 169

<A NAME="RD05103ST-3K">3k</A> Rubinstenn G. Mallet J.-M. Sinaӱ P. Tetrahedron Lett. 1998, 39: 3697

<A NAME="RD05103ST-3L">3l</A> Du Y. Polat T. Linhardt RJ. Tetrahedron Lett. 1998, 39: 5007

<A NAME="RD05103ST-3M">3m</A> Dondoni A. Kleban M. Zuurmond H. Marra A. Tetrahedron Lett. 1998, 39: 7991

<A NAME="RD05103ST-3N">3n</A> Mekai ED. Rubinstenn G. Mallet J.-M. Sinaӱ P. Synlett. 1998, 831

<A NAME="RD05103ST-3O">3o</A> Sazaki M. Fuwa H. Inoue M. Tachibana K. Tetrahedron Lett. 1998, 39: 9027

<A NAME="RD05103ST-3P">3p</A> Patro B. Schmidt RR. Synthesis 1998, 1731

<A NAME="RD05103ST-3Q">3q</A> Jarreton O. Skrydstrup T. Espinosa J.-F. Jiménez-Barbero J. Beau J.-M. Chem.-Eur. J. 1999, 5: 430

<A NAME="RD05103ST-3R">3r</A> Pham-Huu D.-P. Petruová M. Bemiller JN. Petru L. Tetrahedron Lett. 1999, 40: 3053

<A NAME="RD05103ST-3S">3s</A> Postema MHD. Calimente D. Tetrahedron Lett. 1999, 40: 4755

<A NAME="RD05103ST-3T">3t</A> Roy R. Dominique R. Das SK. J. Org. Chem. 1999, 64: 5408

<A NAME="RD05103ST-4A">4a</A> Dyer UC. Kishi Y. J. Org. Chem. 1998, 53: 3383

<A NAME="RD05103ST-4B">4b</A> Wang Y. Goekjian PG. Ryckman DM. Kishi Y. J. Org. Chem. 1998, 53: 4151

<A NAME="RD05103ST-4C">4c</A> Bimbala RM. Vogel P. Tetrahedron Lett. 1991, 32: 1429

<A NAME="RD05103ST-4D">4d</A> Bimbala RM. Vogel P. J. Org. Chem. 1992, 57: 2076

<A NAME="RD05103ST-5A">5a</A> Schmidt RR. Beyerbach A. Liebigs Ann. Chem. 1992, 983

<A NAME="RD05103ST-5B">5b</A> Zhu Y.-H. Vogel P. Tetrahedron Lett. 1998, 39: 31

<A NAME="RD05103ST-5C">5c</A> Gerber P. Vogel P. Tetrahedron Lett. 1999, 40: 3165

<A NAME="RD05103ST-5D">5d</A> Zhu Y.-H. Demange R. Vogel P. Tetrahedron: Asymmetry 2000, 11: 263

<A NAME="RD05103ST-6">6</A> Dawson IM. Johnson T. Paton RM. Rennie AC. J. Chem. Soc., Chem. Commun. 1988, 1339

<A NAME="RD05103ST-7A">7a</A> Dondoni A. Knie˛o L. Martinková M. J. Chem. Soc., Chem. Commun. 1994, 1963

<A NAME="RD05103ST-7B">7b</A> Dondoni A. Knie˛o L. Martinková M. Imrich J. Chem.-Eur. J. 1997, 3: 424

<A NAME="RD05103ST-8">8</A> Knie˛o L. Budì ínsk M. Vojtíek P. Martinková M. Enantiomer 1999, 4: 351

<A NAME="RD05103ST-9A">9a</A> Pasquarello C. Demange R. Vogel P. Bioorg. Med. Chem. Lett. 1999, 9: 793

<A NAME="RD05103ST-9B">9b</A> Pasquarello C. Picasso S. Demange R. Malissard M. Berger EC. Vogel P. J. Org. Chem. 2000, 65: 4251

<A NAME="RD05103ST-10">10</A> Abdel-Rahman AA.-H. El Ashry E.-SH. Schmidt RR. Carbohydr. Res. 1999, 315: 106

<A NAME="RD05103ST-11">11</A> Brenna E. Fuganti C. Grasseli P. Serra S. Zambotti S. Chem.-Eur. J. 2002, 8: 1872

<A NAME="RD05103ST-12">12</A> Dondoni A. Marra A. Merino P. J. Am. Chem. Soc. 1994, 116: 3224

Selected data of compound 4: pale yellow oil; ¹H NMR (500 MHz, CDCl₃): δ (ppm) 8.02 (d, 1 H, J = 2.9 Hz, CH-thiazole); 7.70 (d, 1 H, J = 2.9 Hz, CH-thiazole); 7.41 (d, 1 H, J = 15.7 Hz, H-1a); 7.25 (ddd, 1 H, J = 15.7 Hz, J = 7.1 Hz, J = 3.0 Hz, H-2a); 5.34 (dd, 1 H, J = 9.2 Hz, J = 8.9 Hz, H-3); 5.13 (dd, 1 H, J = 8.9 Hz, J = 5.5 Hz, H-2); 4.96 (dd, 1 H, J = 8.87 Hz, J = 8.80 Hz, H-4); 4.42 (ddd, 1 H, J = 4.9 Hz, J = 4.8 Hz, J = 5.5 Hz, H-1); 4.25 (dd, 1 H, J = 12.2 Hz, J = 6.0, H-6′); 4.04 (dd, 1 H, J = 12.2 Hz, J = 2.1 Hz, H-6); 3.92 (m, H-5); 2.85 (m, 1 H, H-7), 2.63 (m, 1 H, H-7′); 2.06, 2.05, 2.04, 2.00 (s, 4 × 3H, Ac). ¹³C NMR (125 MHz, CDCl₃) δ (ppm) : 180.85 (CO-C=C); 170.55, 196.88, 169.5, 169.41, 169.37 (4 × O=C-CH₃); 167.65 (thiazole C-2); 144.68 and 126.46 (2 × CH-thiazole); 144.62 and 126.46 (2 × -CH=); 71.16 (C-1); 69.87 (C-3); 69.73 (C-2); 69.17 (C-5); 68.40 (C-4); 61.90 (C-6); 29.74(C-7); 20.49, 20.47, 20.44, 20.38 (4 × O=C-CH₃). ESI MS: 676.4 (M + H).

The NOE experiments with the obtained mixture of cycloadducts proved the cis relative configurations on dihydropyran ring in both componds 6 and 7. The NMR spectra did not reveal any endo-cycloadducts in the reaction mixture.

Ethyl vinyl ether (1.5mL, 15 mmol) and Eu(fod)₃ (460 mg, 0.4 mmol) were added to a solution of 5 (4 g, 6.2 mmol) in dichloromethane (10.7 mL) and the reaction mixture was sonicated for 6 h at room temperature. The solvent and the excess ethyl vinyl ether were evaporated. Chromatography of the residue (light petroleum-EtOAc, 8:1) afforded 2.05 g (48%) of compound 8 (R_f = 0.29) and 1.94 g (46%) of compound 9 (R_f = 0.42).
Selected data of compound 8: ¹H NMR (500 MHz, CDCl₃): δ (ppm) 7.83 (d, 1 H, J = 3.3 Hz, CH-thiazole); 7.17-7.32 (m, 21 H, 4 × C₆H₅, CH-thiazole); 6.08 (d, 1 H, J = 3.4 Hz, H-4a); 5.20 (dd, 1 H, J = 2.1 Hz, J = 6.8 Hz, H-1a); 4.96-4.48 (m, 8 H, 4 × C₆H₅-CH ₂); 4.30 (m, 1 H, H-1); 4.02 (dq, 1 H, J = 9.6 Hz, J = 7.0, -O-CH ₂-CH₃); 3.82-3.62 (m, 8 H, H-2, H-3, H-4, H-5, H-6, H-6′, -O-CH ₂-CH₃); 2.62 (m, 1 H, H-3a); 2.17 (ddd, 1 H,, J = 2.1 Hz, J = 4.6 Hz, J = 11.5, H-2a_eq); 1.98 (m, 2 H, H-7, H-7′); 1.88 (ddd, 1 H, J = 6.8 Hz, J = 11.5 Hz, J = 11.5, H-2a_ax); 1.30 (t, 3 H, J = 7.0, -O-CH₂-CH ₃). ¹³C NMR (125 MHz, CDCl₃) δ (ppm): 164.62 (thiazole C-2); 143.73 (C-5a); 143.28 (CH-thiazole); 138.36, 138.27, 138.22, 138.12 (4 × ipso C ₆H₅-CH₂), 128.36-127.57 (20 × C ₆H₅-CH₂); 118.48 (CH-thiazole); 104.24 (C-4a); 99.61 (C-1a); 82.36, 80.13, 78.07, 72.31, 71.48 (C-1, C-2, C-3, C-4, C-5); 75.42, 74.96, 73.53, 73.14 (4 × C₆H₅-CH₂); 69.1 (C-6); 64.65 (O-CH₂-CH₃); 33.76 (C-2a); 30.22 (C-7); 27.67 (C-3a); 15.27 (O-CH₂-CH₃). ESI MS: 748.2 (M + H).
Selected data of compound 9: ¹H NMR (500 MHz, CDCl₃): δ (ppm) 7.82 (d, 1 H, J = 3.3 Hz, CH-thiazole); 7.15-7.38 (m, 21 H, 4 × C₆H₅, CH-thiazole); 5.97 (d, 1 H, J = 3.2 Hz, H-4a); 5.20 (dd, 1 H, J = 1.7 Hz, J = 6.7 Hz, H-1a); 4.97-4.50 (m, 8 H, 4 × C₆H₅-CH ₂); 4.25 (m, 1 H, H-1); 4.05 (dq, 1 H, J = 9.6 Hz, J = 7.0 Hz, O-CH ₂-CH₃); 4.08-3.59 (m, 8 H, H-2, H-3, H-4, H-5, H-6, H-6′, O-CH ₂-CH₃); 2.67 (m, 1 H, H-3a), 2.22 (ddd, 1 H, J = 1.7 Hz, J = 2.6 Hz, J = 13.3 Hz, H-2a_eq); 2.09 (m, 1 H, H-7); 1.87 (m, 1 H, H-7′); 1.75 (ddd, 1 H, J = 6.7 Hz, J = 13.3 Hz, J = 13.3 Hz, H-2a_ax); 1.30 (t, 3 H, J = 7.0 Hz, O-CH₂-CH ₃). ¹³C NMR (125 MHz, CDCl₃) δ (ppm): 164.40 (thiazole C-2); 143.86 (C-5a); 143.29 (CH-thiazole); 138.68, 138.22, 138.04 (4 × ipso C₆H₅-CH₂); 128.49-127.57 (20 × C ₆H₅-CH₂); 118.40 (CH-thiazole); 105.65 (C-4a); 99.85 (C-1a); 82.53, 79.95, 77.99, 71.45, 71.32 (C-1, C-2, C-3, C-4, C-5); 77.56, 76.36, 73.47, 72.83 (4 × C₆H₅-CH₂); 68.89 (C-6); 64.74 (O-CH₂-CH₃); 32.36 (C-2a); 30.16 (C-7); 27.15 (C-3a); 15.28 (O-CH₂-CH₃). ESI MS: 748.2 (M + H).

<A NAME="RD05103ST-16">16</A> Dondoni A. Marra A. Scherrmann M.-C. Bertolasi V. Chem.-Eur. J. 2001, 7: 1371

A solution of aldehyde 10 (230 mg, 0.33 mmol) in tetrahydrofuran (3.4 mL) was cooled to 0 °C and then treated with 1 M solution of (CH₃)₂S˙BH₃ in tetrahydrofuran (0.69 mL, 0.69 mmol). The reaction mixture was stirred for 20 min at 0 °C and for 18 h at room temperature. Then, 0.37 mL of 30% NaOH and 0.37 mL of 30% H₂O₂ were added at 0 °C, and the solution was stirred at room temperature for 40 min. After dilution with brine (10 mL), the solution was extracted with ethyl acetate (3 × 10 mL), and the combined organic layers were dried (Mg₂SO₄). Evaporation of the solvent under reduced pressure and chromatography of the residue (light petroleum-ethyl acetate 1:1) afforded 143 mg (60%) of 12 (R_f = 0.5) as a colorless oil.

Selected data of compound 14: ¹H NMR (CDCl₃) : δ (ppm) 5.25 (dd, 1 H, J = 9.4 Hz, J = 9.4 Hz, H-3); 4.98 (dd, 1 H,
J = 9.4 Hz, J = 5.7 Hz, H-2); 4.93 (dd, 1 H, J = 9.4 Hz, J = 9.2 Hz, H-4); 4.75 (dd, 1 H, J = 9.0 Hz, J = 10.0 Hz, H-4a); 4.52 (dd, 1 H, J = 1.0 Hz, J = 9.4 Hz, H-1a); 4.31-4.20 (m, 4 H, H-1, H-6a, H-6, H-6′); 4.12 (dd, 1 H J = 2.2 Hz, J = 12.1 Hz, H-6a′); 3.95 (m, 1 H, O-CH₂-CH ₃); 3.85 (m, 1 H, H-5); 3.59-3.51 (m, 2 H, H-5a, -O-CH₂-CH ₃); 2.20 (m, 1 H, H-2a_eq.); 2.14-2.04 (m, 19 H, 6 × Ac, H-7); 1.65 (m, 2 H, H-3a, H-7′); 1.54 (m, 1 H, H-2a_ax.); 1.23 (t, 1 H, J = 7.0 Hz, O-CH₂-CH ₃). ¹³C NMR (125 MHz CDCl₃) δ (ppm): 100.74 (C-1a); 74.50 (C-5a); 72.58 (C-1); 71.70 (C-4a); 70.05 (C-2); 69.56 (C-3); 68.77 (C-5); 68.66 (C-4); 64.67 (O-CH₂-CH₃); 62.63 (C-6); 62.38 (C-6a); 37.16 (C-2a); 36.00 (C-7); 27.50 (C-3a); 20.50 (Ac); 15.00 (O-CH₂-CH₃). ESI MS: 627.3 (M + Na).
Selected data of compound 17: ¹H NMR (CDCl₃) : δ (ppm) 5.25 (dd, 1 H, J = 8.9 Hz, J = 8.9 Hz, H-3); 5.09 (dd, 1 H,
J = 9.2 Hz, J = 5.7 Hz, H-2); 4.94 (dd, 1 H, J = 8.9 Hz, J = 8.9 Hz, H-4); 4.74 (dd, 1 H, J = 9.9 Hz, J = 9.9 Hz H-4a); 4.53 (d, 1 H, J = 8.1 Hz, H-1a); 4.33-4.18 (m, 4 H, H-1, H-6a, H-6, H-6′); 4.08 (dd, 1 H, J = 2.3 Hz, J = 12.1 Hz, H-6a′); 3.96 (dq, 1 H, J = 9.2 Hz, J = 7.1 Hz, O-CH ₂-CH₃); 3.82 (m, 1 H, H-5); 3.59-3.51 (m, 2 H, H-5a, O-CH ₂-CH₃); 2.17-2.02 (m, 19 H, 6 × Ac, H-2a_eq.); 1.99-1.87 (m, 2 H, H-7, H-3a); 1.41 (ddd, 1 H,, J = 8.1 Hz, J = 9.7 Hz, J = 12.7 Hz, H-2a_ax.); 1.3-1.18 (m, 1 H, H-7′); 1.24 (t, 3 H, J = 7.1 Hz, -O-CH₂-CH ₃). ¹³C NMR (125 MHz CDCl₃) δ (ppm) : 101.22 (C-1a); 74.51 (C-5a); 70.44 (C-4a); 69.99 (C-3); 69.90 (C-2); 69.11 (C-4); 68.60 (C-5); 68.45 (C-1); 64.66 (O-CH₂-CH₃); 62.80 (C-6a); 62.1(C-6); 35.04 (C-2a); 34.41 (C-3a); 26.57 (C-7); 20.62 (Ac), 14.94 (O-CH₂-CH₃). ESI MS: 627.3 (M + Na).

Crystallographic data for the structure 17 have been deposited with the Cambridge Crystallographic Data Centre; reference number CCDC 203383. Copies of the data can be obtained on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (E-mail: deposit@ccdc.cam.ac.u).