Highly β-Selective Mannosylation towards Manβ1-4GlcNAc Synthesis: TMSB(C6F5)4 as a Lewis Acid/Cation Trap Catalyst

Shin-ichi Tanaka; Mamoru Takashina; Hiroomi Tokimoto; Yukari Fujimoto; Katsunori Tanaka; Koichi Fukase

doi:10.1055/s-2005-872678

LETTER

Highly β-Selective Mannosylation towards Manβ1-4GlcNAc Synthesis: TMSB(C₆F₅)₄ as a Lewis Acid/Cation Trap Catalyst

Shin-ichi Tanaka, Mamoru Takashina, Hiroomi Tokimoto, Yukari Fujimoto, Katsunori Tanaka, Koichi Fukase*
Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043, Japan
Fax: +81(6)68505419; e-Mail: koichi@chem.sci.osaka-u.ac.jp;

Abstract

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Abstract

Highly β-selective mannosylation of 4,6-O-benzylidene-mannopyranosyl-N-phenyltrifluoroacetimidate (α/β, 5:95, 93% yield) has been realized by utilizing a dual Lewis acid/cation trap catalyst, TMSB(C₆F₅)₄. The obtained Manβ1-4GlcNTroc unit can be readily converted to a variety of N-linked oligosaccharides.

Key words

stereoselective mannosylation - β-glycoside - oligosaccharides - Lewis acid - TMSB(C₆F₅)₄ - Manβ1-4GlcNAc synthesis

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References

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Preparation of TMSB(C₆F₅)₄: AgNO₃ (73.9 mg, 0.44 mmol) dissolved in distilled H₂O (2.2 mL) was mixed with a solution of LiB(C₆F₅)₄ (150 mg, 0.220 mmol) in Et₂O (3.3 mL) in a separatory funnel. The biphasic solution was vigorously shaken for 5 min and the organic phase was collected. The solvent was removed in vacuo on a rotary evaporator and the residue was then placed on a vacuum pump for 10 min. To the AgB(C₆F₅)₄ obtained 4 Å MS , Et₂O (2.2 mL), toluene (2.2 mL), and TMSCl (31.7 µL) were added; the resulting mixture was used directly for mannosylation. Similarly, HB(C₆F₅)₄ was prepared by the treatment of AgB(C₆F₅)₄ with t-BuBr in Et₂O-toluene.

α/β-Mannoside 4: To a suspension of 4 Å MS, glycosyl acceptor 3 (20.0 mg, 34.7 µmol), and donor 5 (32.1 mg, 52.2 µmol) in CH₂Cl₂ (1.0 mL) was added TMSB(C₆F₅)₄ (50 mM solution) in toluene-Et₂O (1:1, 0.13 mL) at -78 °C under Ar. After the mixture was stirred at -78 °C for 20 min, the reaction was quenched by the addition of sat. aq NaHCO₃ solution. The resulting mixture was extracted with EtOAc, washed with brine, dried over MgSO₄, filtered, and concentrated in vacuo to give the crude product. The residue was purified by preparative TLC (silica gel; hexane-EtOAc, 7:3) to afford a mixture of α/β-mannoside 4 (32.4 mg, 93%). α-Anomer: ¹H NMR (500 MHz, CDCl₃): δ = 7.51-7.49 (m, 2 H, PhCH), 7.39-7.20 (m, 21 H, PhCH, Bn), 7.15-7.13 (m, 2 H, Bn), 5.94-5.87 (m, 1 H, OCH₂CH=CH₂), 5.61 (s, 1 H, PhCH), 5.29 (dd, J = 17.2, 1.4 Hz, 1 H, OCH₂CH=CH₂), 5.24 (d, J = 1.1 Hz, 1 H, H1′), 5.23 (dd, J = 11.7, 1.1 Hz, 1 H, OCH₂CH=CH₂), 5.08 (d, J = 9.9 Hz, 1 H, NH), 4.87 (d, J = 3.7 Hz, 1 H, H1), 4.80 (d, J = 12.2 Hz, 1 H, PhCH₂), 4.70 (d, J = 11.9 Hz, 1 H, PhCH₂), 4.68 (d, J = 11.3 Hz, 1 H, PhCH₂), 4.63-4.54 (m, 5 H, PhCH₂, Cl₃CCH₂OCO), 4.42 (d, J = 11.9 Hz, 1 H, PhCH₂), 4.24 (d, J = 11.9 Hz, 1 H, PhCH₂), 4.23 (t, J = 8.7 Hz, 1 H, H6a′), 4.19 (dd, J = 12.8, 5.3 Hz, 1 H, OCH₂CH=CH₂), 4.12 (dd, J = 9.6, 4.1 Hz, 1 H, H3′), 4.05 (td, J = 10.2, 3.6 Hz, 1 H, H2), 4.00 (dd, J = 12.9, 6.2 Hz, 1 H, OCH₂CH=CH₂), 3.92 (1 H, H5′), 3.88 (1 H, H4), 3.85 (dd, J = 9.2, 4.2 Hz, 1 H, H6b′), 3.83-3.76 (m, 4 H, H2′, H4′, H6ab), 3.73-3.69 (m, 2 H, H3, H5). HRMS (MALDI-TOF): m/z calcd for C₅₃H₅₆Cl₃NO₁₂ [M + Na]⁺, 1028.2752; found, 1028.2747. β-Anomer: ¹H NMR (500 MHz, CDCl₃): δ = 7.49-7.41 (m, 3 H, PhCH, Bn), 7.39-7.20 (m, 21 H, PhCH, Bn), 7.15-7.13 (m, 1 H, Bn), 5.95-5.87 (m, 1 H, OCH₂CH=CH₂), 5.49 (s, 1 H, PhCH), 5.30 (dq, J = 17.2, 1.5 Hz, 1 H, OCH₂CH=CH₂), 5.23 (dd, J = 11.7, 1.1 Hz, 1 H, OCH₂CH=CH₂), 5.01 (d, J = 10.1 Hz, 1 H, NH), 4.91 (d, J = 3.7 Hz, 1 H, H1), 4.87 (d, J = 12.1 Hz, 1 H, PhCH₂), 4.81 (d, J = 11.9 Hz, 1 H, PhCH₂), 4.78-4.71 (m, 3 H, PhCH₂), 4.66-4.54 (m, 4 H, PhCH₂, Cl₃CCH₂OCO), 4.43 (s, 1 H, H1′), 4.34 (d, J = 12.1 Hz, 1 H, PhCH₂), 4.17 (ddt, J = 12.9, 5.3, 1.4 Hz, 1 H, OCH₂CH=CH₂), 4.08-3.93 (m, 4 H, H4′, H6a′, OCH₂CH=CH₂, H2), 3.77-3.65 (m, 2 H, H5, H2′), 3.60 (t, J = 9.6 Hz, 1 H, H3), 3.56-3.50 (m, 2 H, H6ab), 3.46 (t, J = 10.2 Hz, 1 H, H6b′), 3.37 (dd, J = 9.8, 2.9 Hz, 1 H, H3′), 3.06 (td, J = 9.5, 4.8 Hz, 1 H, H5′). HRMS (MALDI-TOF): m/z calcd for C₅₃H₅₆Cl₃NO₁₂ [M + Na]⁺, 1028.2752; found, 1028.2790.