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Synlett 2017; 28(19): 2619-2623
DOI: 10.1055/s-0036-1589082
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© Georg Thieme Verlag Stuttgart · New York

Catalyst-Free Oxidative [3+2] Cycloaddition of Phenols and Styrenes in the Presence of a 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone/1,1,1,3,3,3-hexafluoropropan-2-ol System

Yunxia Wang*
College of Chemistry & Material Science, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education of China, Northwest University, Xi’an 710127, P. R. of China   Email: wyx27210@nwu.edu.cn
,
Na Cui
College of Chemistry & Material Science, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education of China, Northwest University, Xi’an 710127, P. R. of China   Email: wyx27210@nwu.edu.cn
,
Yu Zhao
College of Chemistry & Material Science, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education of China, Northwest University, Xi’an 710127, P. R. of China   Email: wyx27210@nwu.edu.cn
› Author AffiliationsWe are grateful for financial support from the Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education of China, Science and Technology Program of Xi'an City and Shaanxi Province (2017KW-066).
Further Information

Publication History

Received: 06 May 2017

Accepted after revision: 03 July 2017

Publication Date:
03 August 2017 (online)

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Abstract

A catalyst-free oxidative [3+2] cycloaddition of phenols and styrenes was developed with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as the oxidant and 1,1,1,3,3,3-hexafluoropropan-2-ol as the solvent at room temperature. With this method, a broad range of dihydrobenzofurans were efficiently and quickly obtained from readily available phenols and styrenes.

Key words

phenols - styrenes - cyclization - oxidation - dihydrobenzofurans

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589082.
  • Supporting Information
 

  • References and Notes

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  • 18 Dihydrobenzofurans 3a–q; Typical Procedure A 5 mL cylindrical glass bottle equipped with magnetic stirrer bar was charged with the appropriate phenol 1 (0.15 mmol), styrene 2 (0.3 mmol), and HFIP (1.5 mL). When the phenol and the styrene were completely dissolved in the HFIP, DDQ (1.2 equiv) was gradually added. The mixture was stirred at r.t. for 15 min, and then concentrated under vacuum. The crude product was purified by flash chromatography [silica gel, PE–EtOAc (50:1)]. 5-Methoxy-2-phenyl-2,3-dihydro-1-benzofuran (3a) Yellow oil; yield: 30 mg (88%). 1H NMR (400 MHz, CDCl3): δ = 7.46–7.30 (m, 5 H), 6.83–6.76 (m, 2 H), 6.72 (dd, J = 8.7, 2.6 Hz, 1 H), 5.75 (t, J = 8.8 Hz, 1 H), 3.78 (s, 3 H), 3.61 (dd, J = 15.7, 9.3 Hz, 1 H), 3.21 (dd, J = 15.7, 8.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.3, 153.78, 142.0, 128.7, 128.0, 127.5, 125.8, 113.0, 111.2, 109.2, 84.2, 56.1, 38.9. HRMS (ESI+): m/z [M + Na]+ calcd for C15H14NaO2: 249.0886; found: 249.0888. 2-(4-tert-Butylphenyl)-5-methoxy-2,3-dihydro-1-benzofuran (3f) Pale-yellow solid; yield: 38 mg (89%). 1H NMR (400 MHz, CDCl3): δ = 7.39 (d, J = 8.3 Hz, 2 H), 7.34 (d, J = 8.3 Hz, 2 H), 6.83–6.72 (m, 2 H), 6.69 (dd, J = 8.6, 2.2 Hz, 1 H), 5.71 (t, J = 8.7 Hz, 1 H), 3.76 (s, 3 H), 3.57 (dd, J = 15.7, 9.3 Hz, 1 H), 3.22 (dd, J = 15.7, 8.2 Hz, 1 H), 1.31 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 154.2, 153.8, 151.0, 138.8, 127.7, 125.7, 125.5, 112.9, 111.2, 109.2, 84.2, 56.0, 38.6, 34.6, 31.3. HRMS (ESI+): m/z [M + Na]+ calcd for C19H22NaO2: 305.1512; found: 305.1512. 2-Mesityl-5-methoxy-2,3-dihydro-1-benzofuran (3g) colorless oil; yield: 28 mg (69%). 1H NMR (400 MHz, CDCl3): δ = 6.86 (s, 2 H), 6.80 (s, 1 H), 6.73 (d, J = 8.7 Hz, 2 H), 6.11 (t, J = 10.4 Hz, 1 H), 3.78 (s, 3 H), 3.43 (dd, J = 15.9, 9.9 Hz, 1 H), 3.25 (dd, J = 15.9, 11.0 Hz, 1 H), 2.29 (d, J = 14.9 Hz, 9 H). 13C NMR (100 MHz, CDCl3): δ = 154.1, 153.7, 137.4, 136.7, 133.4, 130.0, 128.0, 113.2, 110.9, 109.4, 81.6, 56.0, 36.4, 20.8, 20.4. HRMS (ESI+): m/z [M + Na]+ calcd for C18H20NaO2: 291.1356; found: 291.1350. 8-Methoxy-5,6,6a,11a-tetrahydrobenzo[b]naphtho[2,1-d]furan (3n) Yellow oil; yield: 26 mg (68%). 1H NMR (400 MHz, CDCl3): δ = 7.61 (d,J = 7.1 Hz, 1 H), 7.40–7.29 (m, 2 H), 7.22 (d,J = 7.1 Hz, 1 H), 6.92 (d, J = 1.8 Hz, 1 H), 6.80–6.71 (m, 2 H), 5.72 (d, J = 8.4 Hz, 1 H), 3.85 (s, 3 H), 3.71 (q, J = 8.0 Hz, 1 H), 2.86–2.66 (m, 2 H), 2.18–2.07 (m, 1 H), 1.94–1.82 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 154.3, 153.5, 138.8, 133.6, 132.5, 130.2, 128.5, 128.3, 126.7, 112.9, 110.8, 109.5, 82.1, 56.1, 41.7, 27.9, 27.7. HRMS (ESI+): m/z [M + Na]+ calcd for C17H16NaO2: 275.1043; found: 275.1044. 5-Ethoxy-2-methyl-2-phenyl-2,3-dihydro-1-benzofuran (3o) White solid; yield: 33 mg (90%); mp 58–59 °C. 1H NMR (400 MHz, CDCl3): δ = 7.50–7.43 (m, 2 H), 7.33 (t, J = 7.6 Hz, 2 H), 7.22 (dd, J = 4.9, 2.2 Hz, 1 H), 6.77 (d, J = 8.5 Hz, 1 H), 6.74–6.65 (m, 2 H), 3.93 (q, J = 7.0 Hz, 2 H), 3.36 (q, J = 15.5 Hz, 2 H), 1.75 (s, 3 H), 1.36 (t, J = 7.0 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 153.4, 153.0, 146.9, 128.3, 127.4, 127.0, 124.5, 113.9, 112.1, 109.4, 89.1, 64.3, 45.2, 29.2, 15.0. HRMS (ESI+): m/z [M + Na]+ calcd for C17H18NaO2: 277.1199; found: 277.1199.