InBr₃-Catalyzed Synthesis of Aryl 1,2-trans-Thio(seleno)glycosides

Abstract

InBr₃ is demonstrated to be an efficient catalyst for reactions of fully acetated aldoses with aryl mercaptans or selenophenol at room temperature, rapidly furnishing the corresponding thioglycosides or selenoglycosides with exclusively 1,2-trans-stereoselectivity. This bromide is an air- and moisture-stable Lewis acid and therefore the reactions can be performed in air atmosphere making the procedure simple to perform.

Key words

InBr₃ - thioglycosides - selenoglycosides - stereoselectivity - aldose acetates

• References and Notes

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• 19 InBr₃-Catalyzed Reaction of Fully Acetylated Aldose with Aryl Thiol; Typical Procedure: To a solution of β-ribofuranose tetraacetate (0.1 mmol) and 4-fluorobenzenethiol (0.12 mmol) in CH₂Cl₂ (2 mL) was added InBr₃ (0.01 mmol) and the reaction mixture was stirred for 2 h at room temperature. Upon completion of the reaction (monitored by TLC), the reaction mixture was concentrated under reduced pressure and the resulting residue was subjected to flash chromatograph (petroleum ether–EtOAc, 4:1) to afford the desired product 1j. Yield: 98%; colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.52 (dd, J = 8.8, 5.2 Hz, 2 H), 7.04 (t, J = 8.7 Hz, 2 H), 5.18–5.24 (m, 3 H), 4.23–4.29 (m, 2 H), 4.10 (dd, J = 12.8, 5.4 Hz, 1 H), 2.11 (s, 3 H), 2.08 (s, 3 H), 2.05 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.4, 169.5, 169.3, 164.4, 161.9, 136.3, 126.3, 116.1, 88.0, 80.1, 73.6, 71.3, 63.3, 20.7, 20.5. HRMS (ESI): m/z [M +H]⁺ calcd for C₁₇H₂₀FO₇S: 387.0914; found: 387.0917.
• 20 InBr₃-Catalyzed Reaction of Fully Acetylated Aldose with Phenylselenol; Typical Procedure: To a solution of β-ribofuranose tetraacetate (0.1 mmol) and phenylselenol (0.12 mmol) in CH₂Cl₂ (2 mL) was added InBr₃ (0.01 mmol) and the reaction mixture was stirred for 1.5 h at room temperature. Upon completion of the reaction (monitored by TLC), the reaction mixture was concentrated under reduced pressure and the resultant residue was rapidly eluted through a short column of silica gel (ethyl acetate–petroleum ether, 30%) to give the desired product 2c. Yield: 97%; colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.64 (d, J = 6.4 Hz, 2 H), 7.38–7.27 (m, 3 H), 5.55 (d, J = 4.0 Hz, 1 H), 5.43–5.38 (m, 1 H), 5.26 (t, J = 5.2 Hz, 1 H), 4.32–4.23 (m, 2 H), 4.12–4.05 (m, 1 H), 2.08 (s, 6 H), 2.07 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.5, 169.6, 169.4, 135.6, 129.2, 128.6, 83.2, 80.0, 75.5, 71.2, 63.2, 20.8, 20.6, 20.5. HRMS (ESI): m/z [M +H]⁺ calcd for C₁₇H₂₁O₇Se: 417.0452; found: 417.0454.