Efficient and Catalyst-Free Michael Addition of d-Glucosamines to Acetylenic and Vinylic Compounds: Access to Vinylogous Carbamates of d-Glucosamine Derivatives

Abstract

An efficient, catalyst-free methodology has been developed for the Michael addition reaction between d-glucosamine derivatives and various Michael acceptors. All reactions proceeded smoothly at room temperature to furnish novel sugar-derived vinylogous carbamates in high chemical yields and excellent stereoselectivity.

Key words

carbohydrates - d-glucopyranosides - sugar amines - acetylene dicarboxylates - vinylic compounds

• References and Notes

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• 13 Experimental Procedure A solution of a d-glucosamine derivative (1–4, 0.2 mmol) and a Michael acceptor (5–9, 0.2 mmol) in MeOH (1 mL) was stirred for the given period of time at r.t. After completion of the reaction, the solution was concentrated under reduced pressure and the crude mixture was subjected to silica gel column chromatography eluting with EtOAc–hexanes (5:95 to 20:80) to obtain pure products 10–13 (solid products 10a,d,e were obtained in pure form after workup without column chromatography). Data for selected compounds are given below. Methyl 2-Deoxy-2[(Z)-1,2-dimethoxycarbonylvinyl)]-amino-4,6-O-(phenylmethylene)-α-d-glucopyranoside (10a) Yield 80 mg (94%), light yellow solid, mp 143–144 °C. IR (KBr): ν_max = 2892, 2919, 1731, 1665, 1605, 1455, 1366, 1265, 1214, 1120, 1050, 913, 860, 741, 699 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 8.20 (d, J = 10.0 Hz, 1 H, NH), 7.48–7.44 (m, 2 H), 7.37–7.33 (m, 3 H), 5.51 (s, 1 H), 5.20 (s, 1 H), 4.83 (d, J = 3.5 Hz, 1 H), 4.32–4.26 (m, 1 H), 4.08 (dt, J = 3.5, 10.0 Hz, 1 H), 3.92 (t, J = 9.5 Hz, 1 H), 3.83–3.81 (m, 4 H), 3.74 (t, J = 10.5 Hz, 1 H), 3.69 (s, 3 H) 3.48 (s, 3 H), 3.08 (s, 1 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 170.3, 164.4, 151.4, 137.1, 129.1, 128.2, 126.2, 101.8, 99.5, 89.8, 81.6, 71.3, 68.9, 62.4, 57.6, 55.7, 52.7, 50.9 ppm. ESI⁺-HRMS: m/z calcd for [C₂₀H₂₅NO₉ + Na]⁺: 446.1421; found: 446.1406. Methyl 2-Deoxy-2[(Z)-1,2-diethoxycarbonylvinyl)]amino-4,6-O-(phenylmethylene)-α-d-glucopyranoside (10b) Yield 90 mg (99%), yellowish viscous liquid. IR (KBr): ν_max = 3440, 2978, 2925, 1728, 1665, 1608, 1465, 1378, 1268, 1220, 1139, 1086, 1043, 991, 860, 760, 691, 604 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 8.18 (d, J = 10.0 Hz, 1 H, NH), 7.48–7.44 (m, 2 H), 7.37–7.33 (m, 3 H), 5.52 (s, 1 H), 5.22 (s, 1 H), 4.83 (d, J = 4.0 Hz, 1 H) 4.31–4.25 (m, 3 H), 4.19–4.12 (m, 2 H), 4.08 (dt, J = 4.0, 10.0 Hz, 1 H), 3.92 (t, J = 6.5 Hz, 1 H), 3.84 (dt, J = 5.0, 10.0 Hz, 1 H), 3.74 (t, J = 11.5 Hz, 1 H) 3.48 (s, 3 H), 2.89 (br, 1 H), 1.33 (t, J = 7.5 Hz, 3 H), 1.27 (t, J = 7.0 Hz, 3 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 169.9, 163.9, 151.6, 137.1, 129.1, 128.2, 126.2, 101.8, 99.6, 90.0, 81.6, 71.2, 68.9, 62.5, 61.9, 59.5, 57.8, 55.7, 14.3, 13.9 ppm. ESI⁺-HRMS: m/z calcd for [C₂₂H₂₉NO₉ + H]⁺: 452.1915; found: 452.1915. Methyl 2-Deoxy-2[(Z)-2-ethoxycarbonylvinyl)]amino-4,6-O-(phenylmethylene)-α-d-glucopyranoside (10c) Yield 50 mg (65%), yellowish viscous liquid. IR (KBr): ν_max = 3423, 2925, 2854, 1660, 1593, 1448, 1386, 1216, 1104, 1050, 909, 739, 697 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.90 (t, J = 11.5 Hz, 1 H, NH), 7.57–7.33 (m, 5 H), 6.68 (dd, J = 13.0, 8.0 Hz, 1 H), 5.54 (s, 1 H), 4.75 (d, J = 3.2 Hz, 1 H), 4.52 (d, J = 8.0 Hz, 1 H), 4.30 (dd, J = 11.5, 5.0 Hz, 1 H), 4.15–4.07 (m, 2 H), 3.96 (t, J = 9.0 Hz, 1 H), 3.87–3.80 (m, 1 H), 3.74 (t, J = 11.5 Hz, 1 H), 3.53–3.47 (m, 1 H), 3.45 (s, 3 H), 3.15 (dt, J = 9.5, 3.5 Hz, 1 H), 1.25 (t, J = 7.5 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 170.8, 151.7, 137.0, 129.1, 128.2, 126.2, 101.9, 99.5, 83.1, 83.1, 70.6, 68.8, 63.6, 62.4, 62.3, 58.8, 55.6, 14.4 ppm. ESI⁺-HRMS: m/z calcd for [C₁₉H₂₅NO₇ + Na]⁺: 402.1523; found: 402.1533. 2-Deoxy-2[(Z)-2-dimethoxycarbonylvinyl)]amino-1,3,4,6-tetra-O-benzyl-α-d-glucopyranoside (12a) Yield 134 mg (99%), yellowish viscous liquid. IR (KBr): ν_max = 3852, 3734, 3473, 3408, 2917, 2860, 1730, 1660, 1617, 1552, 1495, 1365, 1278, 1226, 1100, 1069, 908, 743, 691 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 8.09 (d, J = 10.0 Hz, 1 H, NH), 7.37–7.23 (m, 18 H), 7.17–7.14 (m, 2 H), 5.21 (s, 1 H), 4.85–4.76 (m, 4 H), 4.64–4.50 (m, 4 H), 4.24–4.15 (m, 2 H), 3.77–3.68 (m, 3 H), 3.67 (s, 3 H), 3.57 (s, 3 H), 3.52–3.40 (m, 2 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 170.5, 163.6, 152.6, 138.0, 136.7, 128.3, 128.3, 128.1, 128.0, 127.9, 127.7, 127.6, 127.6, 127.5, 127.4, 101.2, 89.3, 84.0, 77.7, 74.9, 74.9, 74.7, 73.4, 70.7, 68.7, 58.8, 52.1, 50.6 ppm. ESI⁺-HRMS: m/z calcd for [C₄₀H₄₃NO₉ + Na]⁺: 704.2830; found: 704.2822. 2-Deoxy-2[(propionitrile)]amino-1,3,4,6-tetra-O-benzyl-β-d-glucopyranoside (13d) Yield 82 mg (60%) as a yellowish viscous liquid. IR (KBr): ν_max = 3284, 2918, 2858, 1381, 1101, 980, 753, 699 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.40–7.22 (m, 18 H), 7.18–7.09 (m, 2 H), 4.96–4.84 (m, 3 H), 4.81 (d, J = 10.5 Hz, 1 H), 4.71 (d, J = 12.0 Hz, 1 H), 4.64 (d, J = 11.0 Hz, 1 H), 4.56–4.48 (m, 3 H), 3.86–3.60 (m, 5 H), 2.82 (s, 2 H), 2.75 (d, J = 9.5 Hz, 1 H), 2.37–2.30 (m, 2 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 138.6, 138.0, 137.8, 137.0, 128.4, 128.4, 128.3, 128.2, 127.9, 127.8, 127.8, 127.7, 127.6, 127.5, 118.6, 96.6, 82.3, 78.4, 75.7, 74.9, 73.4, 70.7, 69.2, 68.4, 62.1, 43.5, 19.5 ppm. ESI⁺-HRMS: m/z calcd for [C₃₇H₄₀N₂O₅ + Na]⁺: 615.2834; found: 615.2825. 2-Deoxy-2[(but-3-en-2-one)]amino-1,3,4,6-tetra-O-benzyl-α-d-glucopyranoside (13e) Yield 93 mg (77%), yellowish viscous liquid. IR (KBr): ν_max = 3433, 3031, 2922, 2858, 1955, 1876, 1727, 1638, 1565, 1486, 1454, 1356, 1291, 1112, 936, 911, 806, 743, 698 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 9.88 (t, J = 12.0 Hz, 1 H, NH), 7.46–7.40 (m, 2 H), 7.38–7.23 (m, 16 H), 7.19–7.12 (m, 2 H), 6.66 (dd, J = 7.5, 13.0 Hz, 1 H), 5.04 (d, J = 7.5 Hz, 1 H), 4.97 (d, J = 3.5 Hz, 1 H), 4.80 (d, J = 11.0 Hz, 1 H), 4.71 (t, J = 6.5 Hz, 2 H), 4.65–4.55 (m, 3 H), 4.49 (d, J = 11.0 Hz, 2 H), 3.81 (t, J = 9.5 Hz, 2 H), 3.73 (dd, J = 3.5, 10.5 Hz, 1 H), 3.66 (t, J = 9.5 Hz, 1 H), 3.60 (dd, J = 1.5, 10.5 Hz, 1 H), 3.19 (dt, J = 3.5, 10.0 Hz, 1 H), 2.10 (s, 3 H) ppm. ¹³C NMR (125 MHz, CDCl₃): δ = 169.9, 163.0, 151.6, 137.2, 129.1, 128.2, 126.2, 101.9, 99.6, 90.0, 81.6, 71.2, 68.9, 62.5, 61.9, 59.5, 57.8, 55.7, 14.3, 13.9 ppm. ESI⁺-HRMS: m/z calcd for [C₃₈H₄₁NO₆ + Na]⁺: 630.2826; found: 630.2837.
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