Green Synthesis of Diaryl Selenides from Arylboronic Acids and Arylseleninic Acids

Abstract

A new method of deborylative selanylation using arylboronic acids and arylseleninic acids gave diaryl selenoethers and diarylselenoxide. The present approach requires only equimolar arylseleninic acid and led selectively to selenoethers or selenoxides depending on the solvent. The method is metal-free, base- or oxidant-free, efficient, and environmentally friendly.

Key words

seleninic acid - selenoxide - boronic acid - DMSO - diaryl selenide - ipso selanylation

Publikationsverlauf

Eingereicht: 16. November 2021

Angenommen nach Revision: 08. Januar 2022

Accepted Manuscript online:
08. Januar 2022

Artikel online veröffentlicht:
03. Februar 2022

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• 12 General Procedure for the Diarylselenoether Synthesis In a microwave tube were added the arylboronic acid 1 (0.2 mmol), the arylseleninic acid 2 (1 equiv), and DMSO (0.2 mL). The mixture was stirred at 120 °C for 14 h. After cooling at room temperature, 5 mL of water were added, and the product was extracted with ethyl acetate (3 × 5 mL). The organic layers were dried over Na₂SO₄, filtered, and the solvent was evaporated under reduced pressure. Then, the crude product was chromatographed on silica gel with petroleum ether as eluant to obtain pure product 3. (4-Fluoro-3-methyl)(phenyl)selane (3p) Pale yellow oil, yield 45 mg (85%). ¹H NMR (400 MHz, CDCl₃): δ = 7.36–7.41 (m, 3 H), 7.29–7.33 (m, 1 H), 7.23–7.27 (m, 3 H), 6.93 (dd, J = 8.6, 9.4 Hz, 1 H), 2.24 (d, J = 2.0 Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 161.3 (d, J = 246.3 Hz, C), 137.4 (d, J = 5.4 Hz, CH), 133.4 (d, J = 8.0 Hz, CH), 132.1 (C), 132.0 (CH), 129.4 (CH), 127.1 (CH), 126.4 (d, J = 17.6 Hz, C), 116.2 (d, J = 3.7 Hz, C), 14.5 (d, J = 3.6 Hz, CH₃) ppm. HRMS (ESI): m/z calcd for [C₁₃H₁₁FSe + H]⁺: 267.0088; found: 267.0091.
• 13 General Procedure for the Diarylselenoxide Synthesis In a microwave tube were added the arylboronic acid 1 (0.2 mmol), benzeneseleninic acid 2a (1 equiv), and water (0.2 mL). The mixture was stirred at 80 °C for 8 h. After cooling at room temperature, 5 mL of water were added, and the product was extracted with ethyl acetate (3 × 5 mL). The organic layers were dried over Na₂SO₄, filtered, and the solvent was evaporated under reduced pressure. Then, the crude product was chromatographed on silica gel with petroleum ether as eluant to obtain pure product 4. 1-Methoxy-4-(benzeneseleninyl)benzene (4b) White solid, yield 45 mg (78%); mp 56–57 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.66–7.68 (m, 2 H), 8.05 (d, J = 8.8 Hz, 2 H), 7.45–7.48 (m, 3 H), 6.96 (d, J = 8.9 Hz, 2 H), 3.80 (s, 3 H) ppm.¹³C NMR (100 MHz, CDCl₃): δ = 162.2 (C), 142.8 (C), 133.4 (C), 131.3 (CH), 129.7 (CH), 128.3 (CH), 126.3 (CH), 115.3 (CH), 55.5 (CH) ppm. HRMS (ESI): m/z calcd for [C₁₃H₁₂O₂Se + H]⁺: 281.0081; found: 281.0076.