Towards Glucosamine Building Blocks: Regioselective One-Pot Protection and Deallylation Procedures

Abstract

Glucosamine building blocks have been prepared by an efficient regioselective one-pot protection approach. This synthetic route enabled the straightforward preparation of a glucosamine disaccharide in 73% yield. The system Pd(PPh₃)₄/TES was investigated as an alternative procedure for anomeric allyl ether deprotection.

Key words

glucosamine - regioselective protection - one-pot procedure - allyl ether deallylation - palladium catalysis

References and Notes

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All steps involved were previously investigated separately in order to obtain the authentic intermediates samples, to support the TLC monitoring.

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Selected Spectroscopic Data
Compound (7): white solid; mp 63-65 ˚C; [α]_D ^²5 +58.8 (c 0.5, CHCl₃). ^¹H NMR (400 MHz, CDCl₃, 23 ˚C): δ = 7.49-7.26 (m, 10 H, ArH), 5.90 (m, 1 H, CH₂CH=CH₂), 5.23 (d, 1 H, J = 17.4 Hz, CH₂CH=CH ₂), 5.24 (d, 1 H, J = 10.1 Hz, CH₂CH=CH ₂), 5.16 (d, 1 H, J = 9.7 Hz, NH), 4.80-4.70 (m, 3 H, H-1, CH₂CCl₃), 4.67-4.54 (m, 4 H, CH ₂Ph), 4.17 (m, 1 H, CH ₂CH=CH₂), 4.01-3.98 (m, 2 H, H-2, CH ₂CH=CH₂), 3.70-3.60 (m, 5 H, H-4, H-5, H-6a, H-6b, H-3), 2.66 (br s, 1 H, OH). ^¹³C NMR (100 MHz, CDCl₃, 23 ˚C): δ = 54.4, 68.2, 69.8, 70.2, 71.9, 73.6, 74.4, 74.5, 80.1, 95.3, 96.8, 117.9, 127.6, 127.7, 128.4, 128.5, 133.3, 137.7, 138.2, 154.1. HRMS-FAB: m/z calcd for C₂₆H₃₀NCl₃O₇: 574.1166; found: 574.1152.
Compound (8): white solid. ^¹H NMR (400 MHz, CDCl₃, 23 ˚C): δ = 7.40-7.26 (m, 12 H, ArH), 7.05 (d, 2 H, J = 7.5 Hz, ArH), 5.11 (br s, 1 H, NH), 4.90 (d, 1 H, J = 9.7 Hz, H-1), 4.76 (s, 4 H, 2 × CH ₂Ph), 4.57 (dd, 2 H, J = 11.8, 18.2 Hz, CH₂CCl₃), 3.80-3.75 (m, 3 H, 3-H, 2 × H-6), 3.67 (t, 1 H, J = 9.0 Hz, H-4), 3.52-3.50 (m, 1 H, H-5), 3.35 (dd, 1 H, J = 9.0 Hz, 17.6 Hz, H-2), 2.78 (br s, 1 H, OH), 2.30 (s, 3 H, SPhCH ₃).
Compound (10): colorless solid; mp 176-179 ˚C; [α]_D ^²5 +43.3 (c 0.12, CHCl₃). ^¹H NMR (400 MHz, CDCl₃, 23 ˚C): δ = 7.49-7.26 (m, 20 H, ArH), 5.89-5.80 (m, 1 H, CH₂CH=CH₂), 5.42 (s, 1 H, CHPh), 5.28-5.20 (m, 2 H, CH₂CH=CH ₂), 4.95-4.55 (m, 10 H, H-1, 2 × CH ₂Ph, CH ₂Ph, 2 × CH₂CCl₃), 4.29 (d, 1 H, J = 12.1 Hz, CH ₂Ph), 4.13-3.95 (m, 5 H, CH ₂CH=CH₂, H-2, H-1′, H-3′), 3.76-3.44 (m, 6 H, H-6′, H-2′, H-4′, H-3, H-5, H-6), 3.20-3.11 (m, 3 H, H-4, H-5′, H-6′). ^¹³C NMR (100 MHz, CDCl₃, 23 ˚C): δ = 54.6, 57.4, 65.4, 66.8, 68.4, 68.5, 70.2, 73.6, 73.9, 74.5, 76.5, 77.7, 78.0, 82.1, 95.4, 95.5, 96.7, 100.9, 101.1, 118.2, 126.0, 127.2, 127.8, 128.2, 128.3, 128.4, 129.0, 129.8, 133.2, 137.2, 137.7, 138.2, 138.9, 154.0, 154.1. HRMS (ESI-TOF): m/z calcd for C₄₉H₅₂Cl₆N₂O₁₃Na: 1109.1492; found: 1109.1493.

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General Procedure for the Isomerization
To a solution of compound 5 or 11 (0.14 mmol) and Pd(PPh₃)₄ (8 mg, 5 mol%) in dry CH₂Cl₂ (3.2 mL) was added TES (27 µL, 0.17 mmol). After stirring for 24 h at r.t., the reaction mixture was quenched with sat. aq solution of NaHCO₃ (1 mL) and extracted with CH₂Cl₂. The organic layer was washed with brine (1 mL), dried over Na₂SO₄, and concentrated under reduced pressure.
Selected Spectroscopic Data
Compound (13): ^¹H NMR (400 MHz, CDCl₃, 23 ˚C): δ = 7.52-7.28 (m, 10 H, ArH), 6.01 (d, 1 H, J = 4.4 Hz, CH=CHCH₃), 5.59 (s, 1 H, CHPh), 5.25 (d, 1 H, J = 9.3 Hz, NH), 5.04 (d, 1 H, J = 3.6 Hz, H-1), 4.95-4.90 (m, 1 H, CH ₂Ph), 4.67-4.59 (m, 2 H, CH ₂Ph, CH=CHCH₃), 4.34-4.25 (m, 2 H, H-5, H-6), 3.84-3.74 (m, 4 H, H-3, H-2, H-4, H-6), 1.91 (s, 3 H, COCH₃), 1.54 (d, J = 6.9 Hz, 3 H, CH=CHCH ₃). ^¹³C NMR (100 MHz, CDCl₃, 23 ˚C): δ = 10.5, 23.2, 52.4, 63.4, 69.7, 68.8, 74.0, 75.4, 82.7, 98.1, 101.2, 104.8, 125.9, 127.6, 127.8, 128.1, 128.2, 128.4, 128.9, 137.2, 138.3, 141.5, 169.9. HRMS-FAB: m/z calcd for C₂₅H₂₉NO₆Na: 462.1887; found: 462.1658.