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Synlett 2017; 28(02): 201-206
DOI: 10.1055/s-0036-1588624
letter
© Georg Thieme Verlag Stuttgart · New York

Efficient Two-Step Multifunctionalization of Substituted 2-Hydro­xyglycopyranosides

Antonio Franconetti*
a   Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, C/Profesor García González 1, 41012 Sevilla, Spain   Email: afranconetti@us.es   Email: fcabrera@us.es
,
Eleuterio Álvarez
b   Instituto de Investigaciones Químicas, C.S.I.C.-Universidad de Sevilla, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain
,
Francisca Cabrera-Escribano*
a   Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, C/Profesor García González 1, 41012 Sevilla, Spain   Email: afranconetti@us.es   Email: fcabrera@us.es
› Author Affiliations
Further Information

Publication History

Received: 11 July 2016

Accepted after revision: 20 September 2016

Publication Date:
11 October 2016 (online)

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Abstract

A straightforward route to diversely functionalized glycopyranosides is reported. 2,3-Enopyranosides, 2- and/or 3-azido-, 2-halopyranosides, and a hex-3-ulose, among other α- and β-glycopyranosides are easily obtained in good to excellent yields from 2-hydroxyglycopyranosides by means of a two-step process involving trifluoromethanesulfonation and subsequent treatment with the appropriate nucleophilic agent.

Key words

functionalized glycopyranosides - 2-hydroxyglycopyranosides - 2,3-enopyranosides - 2-halopyranosides - DFT calculations - conformational analysis
 

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  • 27 Representative Analytical Data Compound 14: Rf = 0.46 (EtOAc–hexane, 1:4). In agreement with literature data.26 1H NMR (500 MHz, CDCl3): δ = 7.51–7.29 (10 H, m, Ph), 5.67 (1 H, s, H-7), 4.87 and 4.78 (2 H, 2d, J H,H′ = 12.3 Hz, CH2Ph), 4.79 (1 H, dd, J 2,F = 50.4 Hz, J 2,3 = 2.5 Hz, H-2), 4.42 (1 H, d, J 1,F = 18.9 Hz, H-1), 4.36 (1 H, dd, J 6eq,5 = 5.0 Hz, J 6eq,6ax = 10.5 Hz, H-6eq), 4.11 (1 H, dt, J 4,F = 1.8 Hz, J 4,3 = J 4,5 = 9.8 Hz, H-4), 3.91 (1 H, t, J 6ax,6eq = J 6ax,5 = 10.3 Hz, H-6ax), 3.67 (1 H, ddd, J 3,F = 26.4 Hz, J 3,2 = 2.5 Hz, J 3,4 = 9.9 Hz, H-3), 3.57 (3 H, s, OMe), 3.39 (1H, dt, J 5,6eq = 4.9 Hz, J 5,6ax = 9.6 Hz, H-5). 13C NMR (125.7 MHz, CDCl3): δ = 134.6, 129.9, 129.2, 128.9, 128.6, 128.4, 128.1, 126.2 (Ph), 101,8 (C-7), 101.6 (J 1,F = 16 Hz, C-1), 86.2 (J 2,F = 188.7 Hz, C-2), 78.5 (C-4), 75.8 (J 3,F = 25.7 Hz, C-3), 71.7 (CH2Ph), 68.7 (C-6), 67.3 (C-5), 57.6 (OCH3), 50.1 (C-2). HRMS (CI): m/z calcd for C21H23O5F [M]+: 374.1530; found: 374.1527. Compound 15: Rf = 0.67 (EtOAc–hexane, 1:4). 1H NMR (500 MHz, CDCl3): δ = 7.49–7.34 (10 H, m, Ph), 5.60 (1 H, s, H-7), 5.29 (1 H, dd, J 1,F = 49.3, J 1,2 = 0.8 Hz, H-1), 4.89 and 4.75 (2 H, 2 d, J H,H′ = 12.4 Hz, CH2Ph), 4.36 (1 H, dd, J 6eq,5 = 5.0 Hz, J 6eq,6ax = 10.5 Hz, H-6eq), 4.16 (1 H, t, J 4,3 = J 4,5 = 9.6 Hz, H-4), 3.93 (1 H, t, J 6ax,6eq = J 6ax,5 = 10.3 Hz, H-6ax), 3.76 (1 H, m, H-2), 3.67 (4 H, s and m, OMe and H-3, respectively), 3.39 (1 H, dt, J 5,6eq = 4.9 Hz, J 5,6ax = 9.6 Hz, H-5). Compound 18: Rf = 0.47 (EtOAc–hexane, 3:1). IR: νmax = 2114 (N3), 1375, 1141 (SO2), 974 (CF) cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.49–7.27 (5 H, m, Ph), 5.58 (1 H, s, H-7), 4.90 (1 H, d, J 1,2 = 4.1 Hz, H-1), 4.86 (1 H, dd, J 2,3 = J 2,1 = 4.1 Hz, H-2), 4.47 (1 H, dd, J 3,4 = 3.5 Hz, H-3), 4.37 (1 H, dd, J 6ax,6eq = 10.3 Hz, J 6eq,5 = 5.2 Hz, H-6eq), 4.25 (1 H, ddd, J 4,5 = J 5,6ax = 9.9 Hz, H-5), 3.78 (1 H, dd, J 4,3 = 3.5 Hz, J 4,5 = 9.9 Hz, H-4), 3.74 (1 H, dd, J 6ax,6eq = 10.3 Hz, J 6ax,5 = 9.9 Hz, H-6ax), 3.51 (3 H, s, OMe). 13C NMR (125.7 MHz, CDCl3): δ = 136.5–126.3 (Ph), 118.5 (q, J C,F = 319.7, CF3), 102.2 (C-7), 97.2 (C-1), 78.3 (C-2), 77.5 (C-4), 68.8 (C-6), 59.4 (C-3), 58.1 (C-5), 56.8 (OCH3). HRMS (CI): m/z calcd for C15H17F3N3O7S [M + H]+: 440.0739; found: 440.0748. Compound 19: Rf = 0.47 (EtOAc–hexane, 1:4). IR: νmax = 2116 (N3), 1651 (C=C) cm–1. 1H NMR (500 MHz, acetone-d 6): δ = 7.51–7.34 (5 H, m, Ph), 5.77 (1 H, s, H-7), 5.31 (1 H, dd, J 2,1 = 3.0 Hz, J 2,4 = 2.0 Hz, H-2), 5.03 (1 H, dd, J 1,2 = 3.0 Hz, J 1,4 = 1.0 Hz, H-1), 4.58–4.55 (1 H, m, H-5), 4.29 (1 H, dd, J 6eq,6ax = 8.7 Hz, J 6eq,5 = 3.2 Hz, H-6eq), 3.96–3.89 (2 H, m, H-4 and H-6ax), 3.39 (3 H, s, OMe). 13C NMR (125.7 MHz, acetone-d 6): δ = 138.8 (C-3), 138.5-127.0 (Ph), 111.9 (C-2), 102.6 (C-7), 97.3 (C-1), 75.8 (C-5), 69.5 (C-6), 65.0 (C-4), 55.8 (OCH3). HRMS–FAB: m/z calcd for C14H15N3O4 + Na [M]+: 312.0960; found: 312.0955. Compound 22: Yield 85% (112 mg). 1H NMR (500 MHz, CDCl3): δ = 7.63–7.33 (5 H, m, Ph), 6.32 (1 H, d, J H,3 = 9.1 Hz, NH), 5.56 (1 H, s, H-7), 4.92 (1 H, m, H-3), 4.74 (1 H, d, J 1,2 = 3.5 Hz, H-1), 4.33 (1 H, dd, J 4,3 = 4.2 Hz, J 4,5 = 9.7 Hz, H-4), 3.87 (1 H, t, J 2,1 = J 2,3 = 4.0 Hz, H-2), 3.80 (1 H, m, H-5), 3.76 (1 H, t, J 6ax,6eq = J 6ax,5 = 10.1 Hz, H-6ax), 3.66 (1 H, dd, J 6eq,5 = 4.0 Hz, J 6eq,6ax = 9.4 Hz, H-6eq), 3.49 (3 H, s, OMe), 2.06 (3 H, s, COMe). Compound 24: Rf = 0.58 (EtOAc–hexane, 2:1). 1H NMR (500 MHz, CDCl3): δ = 8.21 (1 H, br s, NHAc), 7.52–7.37 (5 H, m, Ph), 5.46 (1 H, t, J 2,1 = J 2,4 = 2.3 Hz, H-2), 5.67 (1 H, s, H-7), 5.03 (1 H, dd, J 1,2 = 3.0 Hz, J 1,4 = 0.7 Hz, H-1), 4.23 (2 H, m, H-4 and H-6eq), 3.90 (1 H, dt, J 5,6eq = 4.4 Hz, J 5,6ax = 10.4 Hz, H-5), 3.84 (1 H, t, J 6ax,6eq = J 6ax,5 = 10.4 Hz, H-6ax), 3.38 (3 H, s, OMe). HRMS (CI): m/z calcd for C16H19NO5 [M]+: 305.1263; found: 305.1260.
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