Copper-Catalyzed Oxidative α-Ketoacylations of Sulfoximines with Aryl Methyl Ketones and Dioxygen as Terminal Oxidant

Abstract

An efficient copper-catalyzed C−H/N−H bond functionalization for the synthesis of α-keto-N-acyl sulfoximines from aryl methyl ketones and NH-sulfoximines with molecular oxygen as terminal oxidant has been developed.

Key words

sulfoximine - ketone - dioxygen - oxidative coupling - α-ketoacylation

• References and Notes

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• 20 Typical Experimental Procedure: A sealed tube (60 mL) was charged with acetophenone (1a, 300 mg, 2.5 mmol), sulfoximine 2a (77.6 mg, 0.5 mmol) and CuBr (14.3 mg, 0.1 mmol, 20 mol%), followed by the addition of DMSO (0.5 mL). The tube was flushed with dioxygen for 1 min and then sealed with a pressure cap. The reaction mixture was vigorously stirred at 80 °C for 24 h. After cooling to ambient temperature, the product was purified by column chromatography using hexane–EtOAc (10:1–2:1) as eluent to give product 3aa. Analytical data of 3aa: white solid, 86% yield; mp 98–99 °C. ¹H NMR (600 MHz, CDCl₃): δ = 8.02 (ddd, J = 15.7, 8.3, 1.0 Hz, 4 H), 7.66–7.71 (m, 1 H), 7.53–7.63 (m, 3 H), 7.43 (t, J = 7.8 Hz, 2 H), 3.45 (s, 3 H). ¹³C{¹H} NMR (150 MHz, CDCl₃): δ = 190.2, 173.3, 137.5, 134.5, 134.2, 132.7, 130.1, 129.9, 128.7, 127.1, 44.8. MS (EI): m/z = 183 (10), 182 (100), 140 (3), 125 (10), 105 (14), 77 (36). HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₄NO₃S: 288.0689; found: 288.0688.
• 21 Applying substrates without an arylketo moiety (pinacolone, 1-cyclohexylethanone, and benzylacetone) did not lead to the expected products. Furthermore, the attempt to use propiophenone remained unsuccessful.
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