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Synlett 2016; 27(18): 2587-2590
DOI: 10.1055/s-0035-1562541
DOI: 10.1055/s-0035-1562541
letter
Synthesis of α-Keto Amides by a Pyrrolidine/TEMPO-Mediated Oxidation of α-Keto Amines
Further Information
Publication History
Received: 04 May 2016
Accepted after revision: 29 July 2016
Publication Date:
16 August 2016 (online)
Abstract
A mild procedure has been developed for the synthesis of α-keto amides by α-oxidation of the corresponding α-keto amines mediated by pyrrolidine and TEMPO. The method can also be applied to the synthesis of α-keto thioamides and α-keto amidines.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1562541.
- Supporting Information
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References and Notes
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- 17 N-(4-Methoxyphenyl)-N-methyl-2-oxo-2-phenylacetamide (2k); Typical Procedure Pyrrolidine (123 μL, 1.5 mmol) was added to a solution of amino ketone 1k (76.5 mg, 0.3 mmol) and TEMPO (4.7 mg, 0.03 mmol) in MeCN (1 mL) under O2 (balloon pressure). The mixture was then stirred at r.t. for 20 h (TLC monitoring) then was concentrated. The residue was purified by column chromatography [silica gel, heptane–EtOAc (5:1)] to give a slightly yellow oil; yield: 63.4 mg (79%); 1H NMR (400 MHz, CDCl3): δ = 7.88–7.77 (m, 2 H), 7.58–7.49 (m, 1 H), 7.45–7.35 (m, 2 H), 7.08–7.00 (m, 2 H), 6.74–6.63 (m, 2 H), 3.68 (s, 3 H), 3.42 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 191.1, 167.1, 158.9, 134.1, 133.5, 133.4, 129.2, 128.6, 128.3, 114.5, 55.2, 36.3; HRMS (ESI): m/z [M + H]+ calcd for C16H16NO3: 270.1130; found: 270.1128.
- 18 (3E)-N-Methyl-2-oxo-N,4-diphenylbut-3-enamide (2j) Slightly yellow oil; yield: 34.6 mg (43%); 1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 16.3 Hz, 1 H), 7.56–7.49 (m, 2 H), 7.47–7.37 (m, 3 H), 7.36–7.26 (m, 3 H), 7.23–7.16 (m, 2 H), 6.77 (d, J = 16.3 Hz, 1 H), 3.45 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 190.1, 167.0, 147.5, 141.7, 134.0, 131.3, 129.6, 129.0, 128.7, 128.1, 126.5, 123.4, 36.5; HRMS (ESI): m/z [M + H]+ calcd for C17H16NO2: 266.1181; found: 266.1179.