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

• 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.
• 10 The reaction of 4-fluorobenzenethiol (1f) with 2a in the presence of Bi(OTf)₃ at 140 °C for 48 h gave 3f in 37% isolated yield.
• 11 Reactions of Other Alcohols with 1aThe reaction of 2-methylprop-2-en-1-ol with 1a under the standard conditions gave no cyclized product, whereas 1-methyl-4-[(2-methylprop-1-en-1-yl)sulfanyl]benzene (CAS 112425–50–0) was obtained in 49% yield. When (2E)-but-2-en-1-ol was used, the cyclized product was obtained in 7% NMR yield (the major product was the diaryl disulfide). When 3-phenylprop-2-en-1-ol or (2E)-1,3-diphenylprop-2-en-1-ol was used, the corresponding ether and diphenyl disulfide were obtained, with no cyclized products.
• 12 Reactions of Other Benzenethiols with 2aThe reaction of 4-methoxybenzenethiol with 2a under the standard reaction conditions gave the corresponding thiochromane 3 in 40% isolated yield. The reaction of 2,5-dimethylbenzenethiol with 2a under the standard reaction conditions gave the corresponding thiochromanes 3 and 4 in NMR yields of 9 and 7%, respectively. The reaction of 3,5-dimethylbenzenethiol with 2a under the standard reaction conditions gave the corresponding 3 and 4, both in NMR yields of 3%.
• 13 The reaction of bis(4-methoxyphenyl) disulfide with 2a under the standard reaction conditions gave the corresponding 3 in 42% isolated yield. The reaction of bis(2-methoxyphenyl)-disulfide with 2a under standard reaction conditions gave the corresponding 3 in 4% NMR yield.
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