Intuition in Medicine

TEMPO-Mediated Aliphatic C–H Oxidation with Oximes and Hydrazones

“…75% yield as a white solid (inseparable E/Z-mixture) from trans-chalcone. The E/Z ratio could not be determined by the 1 H NMR, while likely about 1:1 mixture judged by 13 C NMR. The NMR spectrum were described as a mixture.…”

“…Pure E-isomer: 400MHz, CDCl 3 ) ! 0.91 (3H"1, t, J = 7.6 Hz), 1.01 (3H"0.57, t, J = 7.6 Hz), 1.81 (2H"1, q, J = 7.6 Hz), 2.29 (2H"0.57, q, J = 7.6 Hz), 2.95 (2H"0.57, d, J = 7.6 Hz), 3.07 (2H"1, d, J = 8.0 Hz), 4.33 (2H"0.57, t, J = 7.6 Hz), 4.50 (2H"1, t, J = 8.0 Hz), 7.13-7.28 (10H"1+10H"0.57, m), 9.23 (1H"1+1H"0.57, s br); 13 89% yield (single E-isomer) from 3-(1H-indol-3-yl)-1,3-diphenylpropan-1-one. 11 1 H NMR (400 MHz, DMSO-d 6 ) !…”

“…13 C NMR (100 MHz) spectra on a Bruker Avance 400 spectrometer in CDCl 3 [using CDCl 3 (for 13 C, ! = 77.00) as internal standard] or DMSO-d 6 [using DMSO-d 6 (for 13 C, ! = 39.5) as the internal standard].…”

“…DMF (anhydrous), K 2 CO 3 , TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) and DIAD (diisopropyl azodicarboxylate) were purchased from Sigma-Aldrich Co., Inc. In the case that oximes or hydrazones were obtained as E/Z-mixtures, the stereochemistry was assigned by 13 C NMR (the chemical shift of !-carbon with syn to the OH is farther to the higher field than that with anti to the OH).…”

“…S12 NMR (400 MHz, CDCl 3 ) ! 2.88-2.92 (2H, m), 3.07-3.13 (2H, m), 7.18-7.22 (1H, m), 7.24-7.31 (4H, m), 7.38-7.39 (3H, m), 7.58-7.60 (2H, m), 9.03 (1H, s br);13 C NMR (100 MHz, CDCl 3 ) ! 28.5, 32.2, 126.1, 126.3, 128.3, 128.4, 128.6, 129.3, 135.6, 141.1, 159.1. a white solid (E/Z = 0.75 : 1, inseparable) from 1,2,3-triphenylpropan-1-one.…”