ortho-Amide-Directed Oxidation of Internal Aryl Alkynes Mediated by Cerium(IV) Ammonium Nitrate

Abstract

A fascinating oxidation of alkynes mediated by CAN directed by the amide group to synthesize N-[2-(2-oxo-2-phenylacetyl)phenyl]benzamide derivatives under mild conditions is reported. Excellent yields were obtained with various substituents by this method.

Key Words

CAN - diketones - oxidation - internal aryl alkynes

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• 17 General Procedure A mixture of the substituted N-(2-phenylethynylphenyl)-benzamide 1 with CAN (50 mol%) in MeCN and CH₂Cl₂ as 1:3 ratio under oxygen 1.0133 bar pressure at 28 °C for 24 h, monitored by TLC, extracted with CH₂Cl₂ and H₂O layer was washed with CH₂Cl₂. Combined organic layers were washed with H₂O and brine, dried over anhyd Na₂SO₄, filtered, concentrated, and purified by column chromatography (CH₂Cl₂–hexane, 2:3) to give the corresponding compounds 2. N-[2-(2-Oxo-2-phenylacetyl)phenyl]benzamide (2a) Yellow solid; 92% yield; mp 116–118 °C. ¹H NMR (400 MHz, CDCl₃): δ = 12.33 (NH), 9.10–9.07 (m, 1 H), 8.13–8.10 (m, 2 H), 7.98–7.96 (m, 2 H), 7.71–7.51(m, 9 H), 7.14–7.15 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 199.3, 193.0, 166.1, 142.8, 137.3, 135.2, 134.3, 134.2, 132.7, 132.3, 130.0, 129.2, 129.1, 129.0, 127.5, 127.1, 122.8, 120.9, 118.2. HRMS (EI): m/z calcd for C₂₁H₁₅NO₃Na: 352.0950; found: 352.0948. 4-Methyl-N-[2-(2-oxo-2-phenylacetyl)phenyl]benzamide (2b) Yellow solid; 85% yield; mp 128–130 °C. ¹H NMR (400 MHz, CDCl₃): δ = 12.30 (NH), 9.09–9.07 (m, 1 H), 8.02–7.96 (m, 4 H), 7.72–7.62 (m, 3 H), 7.56–7.52 (m, 2 H), 7.34–7.32 (m, 2 H), 7.13–7.09 (m, 2 H), 7.33 (d, J = 8.4 Hz, 2 H), 7.11 (t, J = 8.0 Hz, 1 H), 2.44 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 199.3, 193.0, 166.2, 143.0, 137.3, 135.1, 134.2, 132.8, 131.5, 130.0, 129.6, 129.2, 127.6, 122.6, 120.9, 118.2, 21.5. HRMS (EI): m/z calcd for C₂₂H₁₇NO₃Na: 366.1106; found: 366.1105.
• 18 CCDC number for compound 2q is CCDC 872227.