Synlett 2022; 33(05): 483-487
DOI: 10.1055/a-1733-7607
letter

Green Synthesis of Diaryl Selenides from Arylboronic Acids and Arylseleninic Acids

,
Vincent Remusat
,
Patrice Vanelle
Aix Marseille Université and the Centre National de la Recherche Scientifique (CNRS) are gratefully acknowledged for financial support.


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.

Supporting Information



Publication History

Received: 16 November 2021

Accepted after revision: 08 January 2022

Accepted Manuscript online:
08 January 2022

Article published online:
03 February 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
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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.