Reaction of Methylenecyclopropanes and Diphenyl Diselenide under Visible-Light Irradiation

Abstract

The reaction of methylenecyclopropanes with diphenyl diselenide promoted by visible light was investigated and a series of 2,4-diphenylselenyl-1-butenes was prepared under mild conditions. Interestingly, with the addition of oxidant such as dibenzoyl peroxide, 1-(phenylselenyl)cyclobutanols were obtained.

Key words

methylenecyclopropanes - selenium - radicals - radical reactions

References and Notes

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8

2,4-Diphenylselenyl-1-butenes 2 - Typical Procedure.
A solution of(diphenylmethylene)cyclopropane (1a, 0.062 g, 0.3 mmol) and diphenyl diselenide (0.094 g, 0.3 mmol) in 5 mL of toluene was irradiated with a tungsten lamp (300 W) under nitrogen atmosphere. The temperature rose to 40 °C because of the irradiation. The reaction was monitored by TLC (eluent: PE). After 3.5 h, the reaction terminated, the solvent was evaporated under vacuum and the residue was subjected to preparative TLC (eluent: PE) to afford 2a (0.135 g, 87%). The melting point and spectra data were consistent with literature.⁶ Other 2,4-diphenylselenyl-1-butenes were prepared in a similar way.

9

1-Phenylselenylcyclobutanol 3 - Typical Procedure. A solution of(diphenylmethylene)cyclopropane (1a, 0.062 g, 0.3 mmol), diphenyl diselenide (0.094 g, 0.3 mmol) and dibenzoyl peroxide (0.073 g, 0.3 mmol) in 5 mL of EtOH was irradiated with a tungsten lamp (300 W) in air. The temperature rose to 40 °C because of the irradiation. The reaction was monitored by TLC (eluent: PE). After 5 h, the reaction terminated, the solvent was evaporated under vacuum and the residue was subjected to preparative TLC (eluent: EtOAc) to afford 3a (0.075 g, 66%). Other 1-(phenylselenyl)cyclobutanols were prepared in a similar way.
Selected Data for 3a: White solid, mp 106-107 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.23-7.57 (m, 15 H), 5.80 (s, 1 H, exchanged with D₂O), 1.26-1.32 (m, 1 H), 0.64-0.70 (m, 2 H), 0.42-0.46 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 6.1, 9.0, 51.1, 81.3, 127.0, 127.1, 127.3, 127.5, 127.7, 128.0, 128.2, 129.1, 131.0, 131.1, 140.1, 143.8. IR (KBr): δ = 3057, 1491, 1044, 806, 745, 703 cm^-1. MS (EI, 70 eV): m/z (%) = 380 (4) [M⁺ + H], 379 (1) [M⁺], 198 (33), 183 (40), 105 (100).