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Synlett 2022; 33(14): 1391-1398
DOI: 10.1055/a-1852-6889
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Organic Chemistry in Thailand

One-Pot Synthesis of Glycosyl Chlorides from Thioglycosides Mediated by a Bromodiethylsulfonium Salt as a Mild Oxidant

Tianchai Chooppawa
a   Green Chemistry for Fine Chemical Production and Environmental Remediation Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
b   Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University Research Building, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
,
Penpicha Janprasert
a   Green Chemistry for Fine Chemical Production and Environmental Remediation Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
,
Panuwat Padungros  ∗
a   Green Chemistry for Fine Chemical Production and Environmental Remediation Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
b   Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University Research Building, Phayathai Road, Pathumwan, Bangkok 10330, Thailand
› Author AffiliationsThis research is supported financially by Thailand Science Research and Innovation Fund Chulalongkorn University (CU_FRB65_bcg (14)_082_23_12 for P.P.). P.P. would like to thank the Chulalongkorn University Office of International Affairs Scholarship for Short-Term Research. T.C. would like to thank the Center of Excellence on Petrochemical and Materials Technology (PETROMAT) for a postdoctoral fellowship.
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Abstract

The conventional synthesis of glycosyl chlorides from thioglycosides relies on sequential oxidation and chlorination. A one-pot synthesis of glycosyl chlorides is warranted as an alternative method. Here, we report a one-pot synthesis of glycosyl chlorides from thioglycoside precursors. The transformation was mediated at low temperatures by bromodiethylsulfonium bromopentachloroantimonate (BDSB) as a mild oxidant with Bu4NCl as an additive. Armed thioglycosides afforded the corresponding α-glycosyl chlorides in moderate to good yields under the optimized conditions. Low conversions and yields were obtained when the less-reactive disarmed thioglycosides were used. Unexpectedly, BDSB-mediated oxidation of thioglycosides without the addition of Bu4NCl also afforded the α-glycosyl chlorides in moderate yields. We suggest a mechanism involving the transfer of chloride ions from the nonnucleophilic bromopentachloroantimonate (SbCl5Br) anion to the oxocarbenium ion.

Keywords

bromodiethylsulfonium bromopentachloroantimonate - thioglycosides - glycosyl chlorides - one-pot synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1852-6889.
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Publication History

Received: 14 February 2022

Accepted after revision: 14 May 2022

Accepted Manuscript online:
14 May 2022

Article published online:
15 June 2022

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  • 31 One-Pot Synthesis of Glycosyl Chlorides from Thioglycosides; General Procedure In a round-bottomed flask, the appropriate thioglycoside (0.1–0.5 mmol) was subjected to three cycles of azeotropic removal of moisture with toluene and acetonitrile in a high-vacuum rotary evaporator. The flask was then added with Bu4NCl (1.8-2.0 equiv), freshly activated 3A MS (0.2-0.5 g), and equipped with a solid-addition funnel containing BDSB (1.8 equiv). The flask was purged and refilled with argon, and anhyd CH2Cl2 was added (1–2 mL, [c] = 0.1 M). The mixture was then stirred at r.t. (27–30 °C) for 30 min then cooled to –70 °C (dry ice/i-PrOH bath). The BDSB was added portionwise from the solid-addition funnel over 5 min, and the mixture was stirred at –70 °C for additional 10 min then allowed to slowly warm to r.t. over 3 h. When the thioglycoside was completely consumed (TLC), sat. aq Na2S2O3 (2 mL) and sat. aq NaHCO3 (2 mL) were added. The mixture was extracted with CH2Cl2 (3 × 5 mL), and the extracts were washed with brine (5 mL), dried (Na2SO4), and concentrated in a rotary evaporator. The crude product was purified by column chromatography (neutralized silica gel, 10% EtOAc–hexanes).2,3,4,6-Tetra-O-benzyl-α-d-glucopyranosyl Chloride (1a)Prepared according to the general procedure (Scheme 3) by using ethyl α-thioglucoside 1 (271 mg, 0.46 mmol), BDSB (458 mg, 0.83 mmol), Bu4NCl (232 mg, 0.83 mmol), freshly activated 3 Å MS (0.5 g), and anhyd CH2Cl2 (4.6 mL, [c] = 0.1 M). After purification, 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl chloride (1a) was obtained as a colorless liquid [yield: 132 mg (51%)], together with 2,3,4,6-tetra-O-benzyl-α-d-glucopyranose (1b) as a colorless liquid [yield: 31 mg (12%)]. The spectroscopic data for 1a and 1b matched those reported in the literature.