A Three-Component, One-Pot, Sequential Synthesis of a Common Tetrasaccharide Block Related to the Lipopolysaccharide of the Escherichia Coli O9, Klebsiella pneumonia O3, and Hafnia alvei PCM 1223

Abstract

An expeditious three-component, one-pot, sequential synthesis of a common block tetrasaccharide fragment Manp-(1→3)-Manp-(1→2)-Manp-(1→2)-Manp related to the pentasaccharide repeating unit of the O-antigen of Escherichia Coli O9, Klebsiella pneumonia O3, and Hafnia alvei PCM 1223 with minimal protecting group manipulation is reported.

Key words

three-component - one-pot - tetrasaccharide - Escherichia coli O9 - Klebsiella pneumonia O3

• References and Notes

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• 18 One-Pot Procedure for the Preparation of Methyl (2-O-Acetyl-3,4,6-tri-O-benzyl-α-d-mannopyranosyl)-(1→3)-(2-O-acetyl-4,6-O-benzylidene-α-d-mannopyranosyl)-(1→2)-(3,4,6-tri-O-benzyl-α-d-mannopyranosyl)-(1→2)-3,4,6-tri-O-benzyl-α-d-mannopyranoside (2): A solution of 3 (58.2 mg, 0.0997 mmol), 4 (40.1 mg, 0.0997 mmol), NMPTC (25.9 mg, 0.1097 mmol), and flame-activated 4 Å MS were stirred in anhydrous CH₂Cl₂ (4 mL) for 0.5 h at room temperature. The reaction mixture was then cooled to –45 °C and stirred for 5 min before TMSOTf (20 μL, 0.1105 mmol) was injected. The temperature was then increased gradually to –10 °C and stirred for 20 min. After the donor 3 was consumed, the reaction temperature lowered to –45 °C and disaccharide acceptor 5 (107.1 mg, 0.1195 mmol) was added. Subsequently, a second portion of NMPTC (28.6 mg, 0.1212 mmol) and TMSOTf (22 μL, 0.1218 mmol) were added. The temperature was then increased gradually from –45 to –10 °C in 0.5 h and the reaction mixture was stirred at –10 °C for an additional 0.5 h. The reaction was quenched with Et₃N (1 mL). The reaction mixture, after dilution with CH₂Cl₂ (10 mL), was filtered through a plug of Celite, and the bed was washed with CH₂Cl₂ (3 × 10 mL). The combined filtrate and washings was concentrated under reduced pressure and the crude mixture was directly purified by silica gel flash column chromatography (hexane–EtOAc, 4:1) to afford 2 (89.4 mg, 54%) as a glassy syrup. R_f = 0.25 (EtOAc–hexane, 20%); [α]_D ²⁶ +25.3 (c 0.94, CHCl₃); ¹H NMR (300 MHz, CDCl₃): δ = 7.37–7.17 (m, 50 H, ArH), 5.62 (s, 1 H, PhCH), 5.52 (dd, J = 5.2, 1.8 Hz, 1 H, H-2′′′), 5.41 (dd, J = 3.5, 1.3 Hz, 1 H, H-2′′), 5.29 (d, J = 1.4 Hz, 1 H, H-1′′′), 5.18 (d, J = 1.2 Hz, 1 H, H-1′), 5.01 (d, J = 1.2 Hz, 1 H, H-1′′), 4.87–4.82 (m, 3 H, H-1, PhCH₂ ), 4.73–4.51 (m, 13 H), 4.48 (d, J = 4.5 Hz, 1 H), 4.40 (dd, J = 9.4, 3.6 Hz, 1 H, H-3′′), 4.30 (d, J = 12.2 Hz, 1 H, PhCH₂), 4.17 (dd, J = 10.0, 3.6 Hz, 1 H, H-6′′), 4.10 (t, J = 2.4 Hz, 1 H, H-2′), 4.06–3.70 (m, 19 H, H-3, H-4, H-5, H-6, H-3′, H-4′, H-5′, H-6a′, H-6b′, H-4′′, H-5′′, H-6′′, H-3′′′, H-4′′′, H-5′′′, H-6a′′′, and H-6b′′′), 3.57 (dd, J = 10.5, 1.5 Hz, 1 H, H-6), 3.22 (s, 3 H, OCH₃), 2.10 (s, 3 H, COCH₃), 2.09 (s, 3 H, COCH₃); ¹³C NMR (75 MHz, CDCl₃): δ = 170.3 (C=O), 169.7 (C=O), 138.7, 138.6, 138.43, 138.34, 138.28, 138.24, 138.1, 137.1, 128.7, 128.4, 128.33, 128.27, 128.2, 128.0, 127.94, 127.88, 127.8, 127.7, 127.63, 127.61, 127.56, 127.52, 127.49, 127.43, 127.39, 126.0, 101.3 (PhCH), 100.6 (C-1′, ¹ J _C––H = 171.6 Hz), 99.9 (C-1′′, ¹ J _C–H = 170.8 Hz), 99.7 (C-1, ¹ J _C–H = 170.4 Hz), 98.9 (C-1′′′, ¹ J _C–H = 178.0 Hz), 79.3, 78.9, 77.7, 77.2, 75.4, 75.2, 75.1, 75.0, 74.9, 74.0, 73.32, 73.27, 72.2, 72.1, 71.7, 71.67, 71.5, 70.9, 69.4, 69.3, 68.6, 68.4, 68.3, 64.1, 54.6, 21.0, 20.9; HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₉₉H₁₀₆O₂₃Na: 1685.7023; found: 1685.7030.