Synlett 2015; 26(14): 2042-2046
DOI: 10.1055/s-0034-1381038
letter
© Georg Thieme Verlag Stuttgart · New York

Photoinduced Synthesis of Benzannulated Spiroketals

Xinzheng Chen*
Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University, Shenzhen University Town, Shenzhen 518055, P. R. of China   Email: xinzheng1943@126.com
,
Sasa Wang
Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University, Shenzhen University Town, Shenzhen 518055, P. R. of China   Email: xinzheng1943@126.com
› Author Affiliations
Further Information

Publication History

Received: 24 March 2015

Accepted after revision: 17 May 2015

Publication Date:
25 June 2015 (online)


Abstract

A range of benzannulated spiroketals were prepared through photoinduced enone isomerization and spiroketalization as key steps. The simple protocol requires no additional reagents or catalyst, and tolerates both moisture and air.

Supporting Information

 
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  • 16 Photoinduced Synthesis of Benzannulated Spiroketals; General Procedure: To a 5 mL flask was added substrate (0.1 mmol) and MeCN (2 mL). The mixture was stirred under irradiation from a household 40 W fluorescent light bulb at ambient temperature. The progress of the reaction was monitored by TLC. Upon consumption of starting materials, the mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography to afford the spiro product. 4′,5′-Dihydro-3′H-spiro[chromene-2,2′-furan] (7a): Yield: 14.8 mg (93%); colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 7.18 (td, J = 8.0, 1.6 Hz, 1 H), 7.13 (dd, J = 7.2, 1.2 Hz, 1 H), 6.95–6.90 (m, 2 H), 6.71 (d, J = 9.6 Hz, 1 H), 5.75 (d, J = 9.6 Hz, 1 H), 4.17–4.12 (m, 1 H), 4.00–3.94 (m, 1 H), 2.42–2.32 (m, 2 H), 2.09–2.00 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 151.7, 129.2, 126.9, 126.8, 122.5, 121.2, 120.3, 116.4, 105.3, 68.2, 39.1, 24.5. HRMS: m/z [M + H]+ calcd for C12H13O2: 189.0916; found: 189.0909. 3′,4′,5′,6′-Tetrahydrospiro[chromene-2,2′-pyran] (20a): Yield: 10 mg (90%); colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 7.21 (td, J = 8.4, 2.0 Hz, 1 H), 7.14 (dd, J = 7.2, 1.2 Hz, 1 H), 7.01 (d, J = 8.0 Hz, 1 H), 6.95 (td, J = 7.6, 1.2 Hz, 1 H), 6.64 (d, J = 9.6 Hz, 1 H), 5.73 (d, J = 9.6 Hz, 1 H), 4.03–3.965 (m, 1 H), 3.64–3.60 (m, 1 H), 2.17–2.11 (m, 2 H), 1.80–1.63 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 151.4, 129.1, 127.0, 126.0, 125.4, 121.4, 121.2, 116.5, 95.4, 61.7, 35.0, 24.7, 18.5. HRMS: m/z [M + H]+ calcd for C13H15O2: 203.1072; found: 203.1067. 3H-Spiro[benzofuran-2,2′-chromene] (22b): Yield: 12.8 mg (80%); white solid. 1H NMR (400 MHz, CDCl3): δ = 7.27–7.17 (m, 4 H), 7.00 (td, J = 7.6, 1.2 Hz, 1 H), 6.98–6.91 (m, 2 H), 6.87 (d, J = 9.6 Hz, 1 H), 6.78 (d, J = 7.6 Hz, 1 H), 5.97 (d, J = 9.6 Hz, 1 H), 3.58 (d, J = 16.8 Hz, 1 H), 3.48 (d, J = 16.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 157.1, 150.9, 129.8, 128.4, 127.5, 127.0, 125.3, 124.4, 122.0, 121.3, 119.7, 116.7, 109.8, 107.7, 43.7. HRMS: m/z [M + H]+ calcd for C16H13O2: 237.0916; found: 237.0909. 6,6′-Diethyl-2,2′-spirobi[chromene] (29c): Yield: 20.7 mg (85%); colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 7.04–7.02 (m, 4 H), 6.81 (d, J = 9.2 Hz, 2 H), 6.77 (d, J = 8.8 Hz, 2 H), 5.96 (d, J = 9.6 Hz, 2 H), 2.61 (q, J = 7.6 Hz, 4 H), 1.23 (t, J = 7.6 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 148.8, 137.5, 129.3, 126.6, 126.1, 121.7, 119.4, 116.5, 95.2, 28.1, 15.8. HRMS: m/z [M + H]+ calcd for C21H21O2: 305.1542; found: 305.1540.