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Synlett 2016; 27(05): 769-772
DOI: 10.1055/s-0035-1560989
DOI: 10.1055/s-0035-1560989
letter
Copper-Catalyzed Oxidative α-Ketoacylations of Sulfoximines with Aryl Methyl Ketones and Dioxygen as Terminal Oxidant
Further Information
Publication History
Received: 20 August 2015
Accepted after revision: 21 October 2015
Publication Date:
11 December 2015 (online)
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.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560989.
- Supporting Information
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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.
- 22 A reaction between phenylglyoxal monohydrate (5) and 2a under air in acetonitrile (instead of DMSO) led to 3aa in 51% yield.
- 23 The fact that compounds 4–6 could not be detected by GC–MS (after 2 h and 4 h) in the standard coupling reaction between 1a and 2a leading to 3aa as well as the observation that the yields of 3aa were comparably low when 4–6 were applied as starting materials (compare Scheme 4, reactions c–e) suggest the involvement of highly reactive transient species, which are difficult to substitute or mimic by pure compounds, being suspected as potential intermediates.
For representative recent reviews and selected examples illustrating the importance of aerobic oxidations, see:
For some selected examples for sulfoximines in Bolm’s group, see: