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An unprecedented lateral sequential lithiation/silylation/condensation of tertiary aromatic amides has been developed that provides an efficient method to build up functional olefins in good yields. In addition, we have established an efficient and simple method that involves UV/Vis, fluorescence, and NMR analyses, to detect the interaction between transition-metal salts and functional olefins containing tertiary amides. This has enabled a highly efficient palladium-catalyzed Suzuki coupling reaction in the presence of tertiary aromatic amide-derived olefin ligands to be developed. The best results were obtained by employing 2 mol-% Pd(OAc)2, 2 equiv. Cs2CO3, a reaction temperature of 80 °C, dioxane as the solvent, and phosphane-free olefin 2d as ligand.

A novel metal-free intramolecular Bronsted-acid-catalyzed domino deprotection–hydrosilylation with hydrosilanes has been developed, and the unexpected Bronsted-acid-catalyzed intermolecular hydrolytic oxidation to functional siloxanes was described for the divergent and facile synthesis of functionalized siloxanes containing aldehyde motifs. We propose that these reactions proceed via neighboring acetal-assisted Si–H bond activation. In addition, a related reaction is expected to open up further opportunities for the development and application of functional organosilicon compounds by organocatalysis.

An unprecedented lateral sequential lithiation/silylation/condensation of tertiary aromatic amides has been developed that provides an efficient method to build up functional olefins in good yields. In addition, we have established an efficient and simple method that involves UV/Vis, fluorescence, and NMR analyses, to detect the interaction between transition-metal salts and functional olefins containing tertiary amides. This has enabled a highly efficient palladium-catalyzed Suzuki coupling reaction in the presence of tertiary aromatic amide-derived olefin ligands to be developed. The best results were obtained by employing 2 mol-% Pd(OAc)2, 2 equiv. Cs2CO3, a reaction temperature of 80 °C, dioxane as the solvent, and phosphane-free olefin 2d as ligand.