Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013 Supporting Information Ruthenium-Catalyzed Ortho C-H Bond Alkylation of Aromatic Amides with α,β- Unsaturated Ketones via a Bidentate-Chelation Assistance Guy Rouquet and Naoto Chatani* Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
[email protected] Contents I. General Information……………………………………………………….S2 II. Materials…………………………………………………………………...S2 III. Optimization Studies………………………………………………………S3-S6 IV. Synthesis of Starting Amides……………………………………………...S7-S8 V. Spectroscopic Data of Starting Amides……………………………….…...S8-S15 VI. Synthesis of Starting α,β-Unsaturated Ketones…………………………....S15-S16 VII. Spectroscopic Data of α ,β-Unsaturated Ketones…………………..………S16-S21 VIII. General Procedure for the Ortho C-H Bond Directed Alkylation………....S21-S22 IX. Spectroscopic Data of Alkylated Products…………………………..…….S22-S57 X. Removal of the 8- Aminoquinoline Directing Group……………………....S58-S65 a) Formation of aldehydes 10………………………………………………S58 b) Spectroscopic Data of Aldehydes 10……………………………………S59-S62 c) Formation of carboxylic acid 12ja……………………………………...S63-S64 XI. Deuterium Labeling Experiments………………………………………....S65-S81 XII. Competition Experiments………………………………………………….S82 XIII. Copies of 1H and 13C NMR Spectra…………………………………….…S83 S1 Electronic Supplementary Material (ESI) for Chemical Science This journal is © The Royal Society of Chemistry 2013 I. General Information 1 13 H NMR and C NMR spectra were recorded on a JEOL ECS-400 spectrometer in CDCl3 or DMSO-d6 with tetramethylsilane as the internal standard. Data are reported as follows: chemical shift in ppm, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, brs = broad singlet, td = triplet of doublets and m = multiplet), coupling constant (Hz), and integration.