Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a 5S1 Conformation

Kazutada Ikeuchi; Shintaro Matsumoto; Daiki Ikuta; Hidetoshi Yamada

doi:10.1055/a-1384-2931

Synlett, Table of Contents

Synlett 2021; 32(08): 817-821
DOI: 10.1055/a-1384-2931

letter

Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a ⁵ S ₁ Conformation

Authors

Kazutada Ikeuchi ∗

^aDepartment of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, 060-0810, Japan

^bSchool of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
Shintaro Matsumoto

^bSchool of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
Daiki Ikuta

^bSchool of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan
Hidetoshi Yamada

^bSchool of Science and Technology, Kwansei Gakuin University, 2-1, Gakuen, Sanda, 669-1337, Japan

Abstract

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Abstract

Generally, glycosylation reactions activate an anomeric substituent in a glycosyl donor to generate an oxocarbenium ion intermediate. Here we report a novel glycosylation reaction triggered by the activation of a 2-O-substituted propargyl group in a 3,6-O-1,1′-[(ethane-1,2-diyl)bibenzene-2,2′-bis(methylene)]-β-thioglucoside. This reaction proceeds through a cationic Au(I)-mediated intramolecular migration of the anomeric substituent onto the alkyne moiety of the propargyl group, followed by α-attack by the hydroxy group in the glycosyl acceptor on the oxocarbenium ion. The migration of the anomeric group occurs selectively through a 6-exo-dig pathway. The 2-(phenylsulfanyl)prop-2-en-1-yl group produced during the glycosylation is removable under conditions similar to those used for removing an allyl group. This reaction will be developed for further applications in orthogonal oligosaccharide synthesis.

Key words

glycosylation - stereoselectivity - propargyl group - gold catalysis - intramolecular migration

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References

References and Notes
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14 Glycoside 19; Typical Procedure (4-F₃CC₆H₄)₃PAuNTf₂ (20 mM) in CH₂Cl₂ (200 μL, 4.0 μmol) was added to a stirred mixture of 13 (20.0 mg, 33.0 μmol), cyclohexylmethanol (5.9 mg, 51 μmol), and activated MS 4 Å (99 mg) in CH₂Cl₂ (1.3 mL) at 0 °C, and the mixture was stirred for 24 h at 0 °C. Sat. aq NaHCO₃ and Et₂O were added, and the mixture was filtered through a cotton–Celite pad to remove the MS. The aqueous filtrate was extracted with Et₂O, and the combined organic layer was washed successively with H₂O and brine. The combined organic layer was dried (Na₂SO₄), filtered, and concentrated, and the residue was purified by column chromatography [silica gel, hexane–EtOAc (15:1 to 9:1)] to give a colorless oil; yield: 20.0 mg (84%, 27.7 μmol, α-form only); [α]_D ²⁴ +34.5 (c 1.47, CHCl₃). IR (ATR): 3063, 3024, 2922, 2853, 1647, 1452, 1323, 1071, 772 cm^–1. ¹H NMR (400 MHz, CDCl₃, 24 °C): δ = 7.46–7.13 (m, 16 H), 7.06 (dd, J = 6.4, 2.8 Hz, 2 H), 5.66 (s, 1 H), 5.22 (s, 1 H), 4.85 (d, J = 3.4 Hz, 1 H), 4.58 (d, J = 10.1 Hz, 1 H), 4.51 (d, J = 11.2 Hz, 1 H), 4.40 (d, J = 11.2 Hz, 1 H), 4.35 (d, J = 11.9 Hz, 1 H), 4.27 (d, J = 10.1 Hz, 1 H), 4.25 (d, J = 14.2 Hz, 1 H), 4.20 (d, J = 11.9 Hz, 1 H), 4.18 (d, J = 14.2 Hz, 1 H), 4.13 (dd, J = 6.6, 3.7 Hz, 1 H), 4.01 (dd, J = 6.6, 3.7 Hz, 1 H), 3.95 (ddd, J = 6.6, 3.7, 2.3 Hz, 1 H), 3.77 (dd, J = 10.7, 3.7 Hz, 1 H), 3.69 (dd, J = 6.6, 3.4 Hz, 1 H), 3.67 (dd, J = 10.7, 2.3 Hz, 1 H), 3.47 (dd, J = 9.4, 6.6 Hz, 1 H), 3.11 (dd, J = 9.4, 6.6 Hz, 1 H), 3.04–2.84 (m, 4 H), 1.72–1.53 (m, 6 H), 1.22–1.01 (m, 3 H), 0.90–0.78 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃, 24 °C): δ = 141.8, 141.7, 140.3, 138.6, 136.2, 135.7, 133.0, 132.5 (2 C), 131.5, 131.0, 129.2 (2 C), 129.1, 129.0, 128.7, 128.4, 128.2 (2 C), 127.9 (2 C), 127.7, 127.4, 126.3, 126.2, 116.5, 96.6, 78.9, 75.1, 74.1, 72.9, 72.9, 72.5, 72.1, 71.5, 69.7, 66.4, 37.9, 33.5, 33.4, 30.1 (2 C), 26.7, 26.0, 25.9. HRMS (ESI): m/z [M + Na]⁺ calcd for C₄₅H₅₂NaO₆S: 743.3382; found: 743.3379.
15 Application of the established conditions to phenylsulfanyl 3,4,6-O-tribenzyl-2-O-proparygyl-β-d-glucopyranose resulted in almost no reaction, indicating that the presence of the EDB group is essential for this glycosylation reaction.
16 See the Supporting Information (SI-8) for the yields of 24 and 25. In cases when 13 was recovered, its yield is also reported.

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Supplementary Material

Supporting Information (PDF)

Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a 5 S 1 Conformation

Authors

Glycosylation by Alkyne Activation of the 2-O-Substituted Propargyl Group in a β-Phenylthioglucoside with a ⁵ S ₁ Conformation