Bismuth Triflate Catalyzed Intermolecular Cyclization of Thiophenols with Allylic Alcohols

Abstract

The catalytic intermolecular cyclization of thiophenols with allylic alcohols in the presence of bismuth triflate afforded the corresponding thiochromane derivatives in a one-pot reaction. The Bi(OTf)₃-catalyzed reaction was also applied to the intermolecular cyclization of diaryl disulfides with 3-methylbut-2-en-1-ol to produce the corresponding thiochromanes.

Key word

S-heterocycles - bismuth catalysis - one-pot reaction - thiochromanes - thiophenols - allylic alcohols

Publication History

Received: 06 April 2024

Accepted after revision: 23 April 2024

Accepted Manuscript online:
23 April 2024

Article published online:
06 May 2024

• References and Notes

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• 9 4,4,6-Trimethylthiochromane (3a): Typical ProcedureA vial was charged with 4-methylbenzenethiol (1a: 12.4 mg, 0.1 mmol), Bi(OTf)₃ (3.3 mg, 5.0 mol% based on 1a), and 3-methylbut-2-en-1-ol (2a; 86.2 mg, 1.0 mmol) under air, and the mixture was stirred at 140 °C for 16 h. The resultant mixture was then diluted with H₂O and extracted with EtOAc. The organic layers were combined, dried (Na₂SO₄), and concentrated under reduced pressure. The residue was purified by preparative TLC (Wakogel B-5F, hexane) to give a pale-yellow oil; yield 18.5 mg (94%; 3a/4a = 84:16, as determined by ¹H NMR analysis of the crude reaction mixture). ¹H NMR (600 MHz, CDCl₃): δ = 7.16 (d, J = 1.4 Hz, 1 H), 6.97 (d, J = 8.3 Hz, 1 H), 6.85 (dd, J = 8.3, 1.4 Hz, 1 H), 3.02–3.00 (m, 2 H), 2.27 (s, 3 H), 1.96–1.94 (m, 2 H), 1.32 (s, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 141.8, 133.5, 128.0, 127.2, 126.9, 126.4, 37.9, 32.9, 30.2, 23.0, 21.1. HRMS (EI); m/z [M⁺] calcd for C₁₂H₁₆S: 192.0973; found: 192.1009.
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