Visible-Light-Promoted Difunctionalization of Olefins Leading to α-Thiocyanato Ketones

Abstract

A simple and convenient visible-light-induced difunctionalization of alkenes with ammonium thiocyanate and dioxygen has been developed at room temperature. A series of α-thiocyanato ketones could be easily and efficiently obtained in moderate to good yields through the formation of C–S and C=O bonds simply by using nontoxic and inexpensive Na₂-Eosin Y as a photocatalyst.

Key words

visible-light catalysis - difunctionalization - alkenes - ammonium thiocyanate - α-thiocyanato ketones

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• 16 Preparation of 1-Phenyl-2-thiocyanatoethanone (4a) To a solution of NH₄SCN (2) (30.4 mg, 0.4 mmol) and Na₂-EosinY (2.8 mg, 0.004 mmol, 2 mol%) in CH₃CN (5 mL) was added alkene 1a (20.8 mg, 0.2 mmol). The reaction mixture was stirred under the irradiation of 3W blue LED under an oxygen atmosphere at r.t. for 5 h. After completion of the reaction, the solution was concentrated under vacuum. The residue was purified by using a mixture of ethyl acetate and petroleum ether (1:10) as eluent to give the desired product 4a. Yield: 30 mg (79%). ¹H NMR (CDCl₃, 500 MHz, ppm): δ = 7.95 (d, J = 8.0 Hz, 2 H), 7.68 (t, J = 7.3 Hz, 1 H), 7.54 (t, J = 7.7 Hz, 2 H), 4.75 (s, 2 H). ¹³C NMR (CDCl₃, 125 MHz, ppm): δ = 190.8, 134.8, 134.0, 129.2, 128.5, 111.9, 43.0. HRMS: m/z [M + Na]⁺ calcd for C₉H₇NOSNa: 200.0146; found 200.0149.