Easy Access to Configurationally
Controlled C-Glycofuranoside-Based Building
Blocks by Means of Formyl C-Glycofuranosides

Yolanda Vera-Ayoso; Pastora Borrachero; Francisca Cabrera-Escribano; Manuel Gómez-Guillén; Joaquim Caner; Jaume Farrás

doi:10.1055/s-0029-1218552

LETTER

Easy Access to Configurationally Controlled C-Glycofuranoside-Based Building Blocks by Means of Formyl C-Glycofuranosides

Yolanda Vera-Ayoso^a, Pastora Borrachero^a, Francisca Cabrera-Escribano*^a, Manuel Gómez-Guillén^a, Joaquim Caner^b, Jaume Farrás^b
^a Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, Apartado de Correos No. 1203, 41071 Sevilla, Spain
Fax: +34(95)4624960; e-Mail: fcabrera@us.es ;
^b Departamento de Química Orgánica, Universidad de Barcelona, Av. Diagonal 647, 08028 Barcelona, Spain

Abstract

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Abstract

A general approach to enantiopure C-glycofuranoside-based hybrid α/β-amino acids and nitrones, among other valuable building blocks, has been established via formyl C-glycofuranosides, easily available from hexose-derived equatorial-2-OH-glycopyranosides by DAST-promoted ring contraction.

Key words

C-glycofuranoside-based building blocks - formyl C-glycofuranosides - DAST-promoted ring contraction - C-glycofuranosyl nitrones - C-glycofuranosyl amino acids

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References

References and Notes

<A NAME="RD27109ST-1A">1a</A> Taylor EA. Clinch K. Kelly PM. Li L. Evans GB. Tyler PC. Schramn VL. J. Am. Chem. Soc. 2007, 129: 6984

<A NAME="RD27109ST-1B">1b</A> Pellisier H. Tetrahedron 2005, 61: 2947

<A NAME="RD27109ST-1C">1c</A> Schmieg J. Yang G. Franck RW. Tsuji MO.
J. Exp. Med. 2003, 198: 1631

<A NAME="RD27109ST-1D">1d</A> Levy W. Chang D. The Chemistry of C-Glycosyl Compound Elsevier; Cambridge: 1995.

<A NAME="RD27109ST-2A">2a</A> Kaliappan KP. Subrahmanyam AV. Org. Lett. 2007, 9: 1121

<A NAME="RD27109ST-2B">2b</A> Moreno B. Quehen C. Rose-Helene M. Leclerc E. Quirion J.-C. Org. Lett. 2007, 9: 2477

<A NAME="RD27109ST-2C">2c</A> Taillefumier C. Chapleur Y. Chem. Rev. 2004, 104: 263

<A NAME="RD27109ST-3A">3a</A> Vera-Ayoso Y. Borrachero P. Cabrera-Escribano F. Carmona AT. Gómez-Guillén M. Tetrahedron: Asymmetry 2005, 16: 889

<A NAME="RD27109ST-3B">3b</A> Vera-Ayoso Y. Borrachero P. Cabrera-Escribano F. Carmona AT. Gómez-Guillén M. Tetrahedron: Asymmetry 2004, 15: 429

<A NAME="RD27109ST-3C">3c</A> Borrachero P. Cabrera-Escribano F. Carmona AT. Gómez-Guillén M. Tetrahedron: Asymmetry 2000, 11: 2927

<A NAME="RD27109ST-3D">3d</A> Borrachero P. Cabrera-Escribano F. Gómez-Guillén M. Madrid-Díaz F. Tetrahedron Lett. 1997, 38: 1231

<A NAME="RD27109ST-4">4</A> One of most important principles of Green Chemistry is that of atom economy. Rearrangements are considered as atom economic reactions: Anastas Y. Warner JC. Green Chemistry: Theory and Practice Oxford University Press; New York: 1998.

<A NAME="RD27109ST-5">5</A> Kirchning A. Kujat C. Luiken S. Schaumann E. Eur. J. Org. Chem. 2007, 2387

<A NAME="RD27109ST-6">6</A> Vera-Ayoso Y. Borrachero P. Cabrera-Escribano F. Gómez-Guillén M. Vogel P. Synlett 2006, 45

<A NAME="RD27109ST-7A">7a</A> Aye Y. Davies SG. Garner C. Roberts PM. Smith AD. Thomson JE. Org. Biomol. Chem. 2008, 6: 2195

<A NAME="RD27109ST-7B">7b</A> Benedek G. Palkó M. Wéber E. Martinek TA. Forró E. Fülöp F. Eur. J. Org. Chem. 2008, 3724

<A NAME="RD27109ST-7C">7c</A> Forró E. Fülöp F. Chem. Eur. J. 2007, 13: 6397

<A NAME="RD27109ST-8A">8a</A> Sharma GVM. Babu BS. Chatterjee D. Ramakrishna KVS. Kunwar AC. Schramm P. Hofmann H.-H. J. Org. Chem. 2009, 74: 6703

<A NAME="RD27109ST-8B">8b</A> Choi SH. Guzei IA. Spencer LC. Gellman SH. J. Am. Chem. Soc. 2008, 130: 6544

<A NAME="RD27109ST-8C">8c</A> Prabhakaran P. Kale SS. Puranik VG. Rajamohanan PR. Chetina O. Howard JAK. Hofmann H.-J. Sanjayan GJ. J. Am. Chem. Soc. 2008, 130: 17743

<A NAME="RD27109ST-8D">8d</A> Schmitt MA. Choi SH. Guzei IA. Gellman SH. J. Am. Chem. Soc. 2006, 128: 4538

<A NAME="RD27109ST-9A">9a</A> Seebach D. Gardiner J. Acc. Chem. Res. 2008, 41: 1366

<A NAME="RD27109ST-9B">9b</A> Sadowsky JD. Schmitt MA. Lee HS. Umezawa N. Wang S. Tomita Y. Gellman SH. J. Am. Chem. Soc. 2005, 127: 11966

<A NAME="RD27109ST-10">10</A> Fülöp F. Martinek TA. Tóth GK. Chem. Soc. Rev. 2006, 35: 323

<A NAME="RD27109ST-11A">11a</A> Stanley LM. Sibi MP. Chem. Rev. 2008, 108: 2887

<A NAME="RD27109ST-11B">11b</A> Ratner DM. Adams EW. Disney MD. Seeberger PH. ChemBioChem 2004, 5: 1375

<A NAME="RD27109ST-12">12</A> Baer HH. Gan Y. Carbohydr. Res. 1991, 210: 233

Preparation and More Relevant Data of Compound 10
A soln of 9 (105 mg, 0.340 mmol) in dry THF (4.8 mL) containing 3 Å MS was treated with NaCNBH₃ (273 mg, 4.35 mmol). The mixture was stirred for 15 min, and then Et₂O-HCl (3.5%, 6 mL) was added. After 5 min, the reaction was diluted with H₂O (20 mL) and CH₂Cl₂ (20 mL). After separation, the organic layer was successively washed with sat. aq NaHCO₃ (50 mL) and brine (50 mL), dried (Na₂SO₄), and concentrated. Column chromatography (hexane-EtOAc, 3:1) gave pure 10 (64 mg, 64%).
Analytical Data
[α]_D ^²4 +16.2 (c 0.63, CH₂Cl₂). IR: ν_max = 2108 (N₃) cm^-¹. ^¹H NMR (500 MHz, acetone-d ₆): δ = 7.36-7.26 (m, 5 H, Ph), 4.75 (s br, 1 H, OH_C4), 4.55 (s, 2 H, CH₂Ph), 4.55-4.53 (m, 1 H, H-4), 4.17 (ddd, 1 H, J _1,2 = J ₁ _′ _,2 = 5.7 Hz, J _2,3 = 3.7 Hz, H-2), 4.14 (dd, 1 H, J _3,4 = 4.2 Hz, H-3), 3.93 (ddd, 1 H, J _4,5 = 7.5 Hz, J _5,6 _′ = 4.5 Hz, J _5,6 = 3.0 Hz, H-5), 3.65 (dd, 1 H, J _6,6 _′ = 11.0 Hz, H-6), 3.58 (dd, 1 H, H-6′), 3.56 (dd, 1 H, J _1,1 _′ = 10.0 Hz, H-1), 3.43 (dd, 1 H, H-1′), 3.31 (s, 3H, OCH₃) ppm. HRMS (CI): m/z calcd for C₁₄H₁₉N₃O₄ + H: 294.1454; found: 294.1462.

The calculations were performed at the University of Barcelona. Lowest-energy conformer were calculated by performing Monte Carlo conformational searches (50000 steps) with MacroModel 8.5 (MM2*, CHCl₃, GB/SA):

<A NAME="RD27109ST-14A">14a</A> Mohamadi F. Richards NGJ. Guida WC. Liskamp R. Lipton M. Caufied C. Chang G. Hendrickson T. Still WC. J. Comp. Chem. 1990, 11: 440

<A NAME="RD27109ST-14B">14b</A> Still WC. Tempczyk A. Hawley RC. Hendrickson T. J. Am. Chem. Soc. 1990, 112: 6127

<A NAME="RD27109ST-15">15</A> Borrachero P. Cabrera F. Diánez MJ. Estrada MD. Gómez-Guillén M. López-Castro A. Moreno J. Paz J. Pérez-Garrido S. Tetrahedron: Asymmetry 1999, 10: 77

The ratio of 24/25 was calculated by the ^¹H NMR (CDCl₃) of the mixture, in particular from the signals of H-4 of both stereoisomers: δ = 5.65 ppm (dd, 1 H, J _4,5 = 7.8 Hz, J _3,4 = 4.5 Hz, H-4) observed for the major stereoisomer 24, and that observed at δ = 4.80 ppm (dd, 1 H, J _4,5 = 7.2 Hz, J _3,4 = 4.8 Hz, H-4) for 25.

<A NAME="RD27109ST-17">17</A> Torres-Sánchez MI. Borrachero P. Cabrera-Escribano F. Gómez-Guillén M. Angulo-Álvarez M. Sánchez E. Favre S. Vogel P. Tetrahedron 2007, 18: 1089

More Relevant Data Compound 16: [α]_D ^²¹ +37 (c 0.77, acetone). ^¹H NMR (500 MHz, acetone-d ₆): δ = 7.36-7.33 (m, 5 H, Ph), 7.09 (d, 1 H, J _NH,3 = 7.0 Hz, CCONH), 6.43 (s br, 1 H, OCONH), 4.58-4.53 (m, 1 H, H-3), 4.57 and 4.58 (each 2 d, 1 H, J _H,H _′ = 12.9 Hz, CH₂Ph), 4.45 (d, 1 H, J _OH,4 = 8.0 Hz, OH_C4), 4.31 (ddd, 1 H, J _2,3 = 8.0 Hz, J ₁ _′ _,2 = 4.5 Hz, J _1,2 = 3.0 Hz, H-2), 4.17-4.14 (m, 1 H, H-4), 4.01 (ddd, 1 H, J _5,6 = J _5,6 _′ = 4.0 Hz, J _4,5 = 3.0 Hz, H-5), 3.77 (dd, 1 H, J _gem = 16.5 Hz, J _NH,CH2a = 6.0 Hz, NHCH ^a ₂), 3.72 (dd, 1 H, J _NH,CH2b = 6.0 Hz, NHCH ^b ₂), 3.55 (dd, 1 H, J _6,6 _′ = 10.5 Hz, H-6), 3.52 (dd, 1 H, H-6′), 3.50 (dd, 1 H, J _1,1 _′ = 10.5 Hz, H-1), 3.40 (dd, 1 H, H-1′), 3.35 (s, 3 H, OCH₃), 1.43 [s, 9 H, C(CH₃)₃] ppm. ^¹³C NMR (125.7 MHz, acetone-d ₆): δ = 170.5, 157.0, 139.6-128.2, 85.2, 79.6, 78.9, 73.8, 73.1, 72.9, 72.0, 59.3, 53.9, 44.9, 28.6 ppm. HRMS (CI): m/z calcd for C₂₁H₃₂N₂O₇ + H: 425.2288; found: 425.2291. Anal. Calcd for C₂₁H₃₂N₂O₇: C, 59.42; H, 7.60; N, 6.60. Found: C, 59.12; H, 7.45; N, 6.72.
Compound 20: [α]_D ^²4 +52 (c 0.66, CH₂Cl₂). IR: ν_max = 2114 (N₃) cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.07 (dd, 1 H, J _NH,CH2a = 5.0 Hz, NH), 5.22 (dd, 1 H, J _4,5 = 8.5 Hz, J _3,4 = 4.5 Hz, H-4), 4.68 (dd, 1 H, J _2,3 = 4.5 Hz, H-3), 4.62 (d, 1 H, H-2), 4.40-4.36 (m, 1 H, H-5), 4.36 (dd, 1 H, J _6,6 _′ = 12.5 Hz, J _5,6 = 2.5 Hz, H-6), 4.23 (q, 2 H, J = 7.0, C₂H₅), 4.13 (dd, 1 H, J _5,6 _′ = 4.0 Hz, H-6′), 4.11 (dd, 1 H, J _gem = 18.0 Hz, NHCH ^a ₂), 4.07 (dd, 1 H, NHCH ^b ₂), 2.16, 2.09 (2 s, each 3 H, COCH₃), 1.29 (t, 3 H, C₂H₅) ppm. HRMS (CI): m/z calcd for C₁₄H₂₀N₄O₈ + H: 373.1359; found: 373.1349.
Compound 22: [α]_D ^²4 -1.2 (c 0.75, CH₂Cl₂). IR: ν_max = 2112 (N₃) cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.41 (s, 5 H, Ph), 6.79 (d, 1 H, J _1,2 = 4.5 Hz, H-1), 5.20 (dd, 1 H, J _4,5 = 8.0 Hz, J _3,4 = 5.0 Hz, H-4), 5.15 (dd, 1 H, J _2,3 = 4.5 Hz, H-2), 4.94 (dd, 1 H, H-3), 4.91 (s, 2 H, CH₂Ph), 4.34 (dd, 1 H, J _6,6 _′ = 12.0, J _5,6 = 3.0 Hz, H-6), 4.24 (ddd, J _5,6 _′ = 4.5 Hz, H-5), 4.04 (dd, 1 H, H-6′), 2.14, 2.08 (2 s, each 3 H, 2 COCH₃) ppm. ^¹³C NMR (125.7 MHz, CDCl₃): δ = 170.7, 170.2, 136.2, 132.0-129.2, 77.2, 77.0, 73.5, 69.3, 63.3, 62.7, 20.9, 20.4 ppm. HRMS (CI): m/z calcd for C₁₇H₂₀N₄O₆ + H: 377.1461; found: 377.1454.