Temperature-Controlled Synthesis of Thiophenol-VBXs from EBXs and Thiophenols

Abstract

Vinylbenziodoxolones (VBXs) are important electrophilic alkene synthons. However, the synthesis of cis-thiophenol-VBX reagents from ethynylbenziodoxolones (EBXs) and thiophenols remains challenging. Herein, we explore an efficient method for the synthesis of cis-thiophenol-VBXs in excellent yield with excellent regio- and stereoselectivities from EBXs and thiophenols under temperature-controlled conditions.

Key words

vinylbenziodoxolones - ethynylbenziodoxolones - iodine(III) - thiophenols - temperature control

Publikationsverlauf

Eingereicht: 12. Juni 2024

Angenommen nach Revision: 31. Juli 2024

Accepted Manuscript online:
31. Juli 2024

Artikel online veröffentlicht:
30. August 2024

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• 15 Typical Procedure and Characterization Data for 3a: Compound 1a (0.2 mmol, 1.0 equiv), ethanol (2 mL), and Et₃N (0.3 mmol, 1.5 equiv) were added to a flask. The mixture was cooled at –50 °C in a low-temperature reactor. 4-Methylthiophenol 2a (0.22 mmol, 1.1 equiv) was added and the reaction mixture was stirred at –50 °C until 1a was consumed (monitored by TLC). The solvent was removed under reduced pressure and the crude product was purified by flash column chromatography on silica gel (CH₂Cl₂/MeOH) to give pure product 3a (97%, 91.6 mg) as a white solid; mp 162.7–163.5 °C. R_f = 0.30 (CH₂Cl₂/MeOH, 20:1). ¹H NMR (600 MHz, DMSO-d ₆): δ = 8.14 (d, J = 7.3 Hz, 1 H), 7.74 (t, J = 7.5 Hz, 1 H), 7.69 (d, J = 8.3 Hz, 1 H), 7.65 (t, J = 7.3 Hz, 1 H), 7.63–7.59 (m, 3 H), 7.31 (d, J = 6.3 Hz, 3 H), 7.09 (d, J = 7.8 Hz, 2 H), 6.95 (dd, J = 8.3, 2.8 Hz, 2 H), 2.10 (d, J = 3.5 Hz, 3 H). ¹³C NMR (150 MHz, DMSO-d ₆): δ = 166.19, 157.44, 138.26, 136.94, 135.11, 134.17, 132.31, 132.10, 130.96, 130.56, 130.39, 129.35, 129.15, 128.78, 128.64, 127.89, 115.73, 109.95, 21.04. HRMS: m/z [M + Na]⁺ calcd for C₂₂H₁₇IO₂S: 494.9886; found: 494.9890.