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(Ar-tpy)Ruᴵᴵ(ACN)₃: A Water-Soluble Catalyst for Aldehyde Amidation, Olefin Oxo-Scissoring, and Alkyne Oxygenation

Joarder, Dripta De, Gayen, Subrata, Sarkar, Rajarshi, Bhattacharya, Rajarshi, Roy, Sima, Maiti, Dilip K.
Journal of organic chemistry 2019 v.84 no.13 pp. 8468-8480
acids, aldehydes, alkynes, amides, carbon-hydrogen bond activation, catalysts, catalytic activity, chemical reactions, chemical structure, ketones, olefin, organic chemistry, ruthenium, water solubility
The synthetic chemists always look for developing new catalysts, sustainable catalysis, and their applications in various organic transformations. Herein, we report a new class of water-soluble complexes, (Ar-tpy)Ruᴵᴵ(ACN)₃, utilizing designed terpyridines possessing electron-donating and -withdrawing aromatic residues for tuning the catalytic activity of the Ru(II) complex. These complexes displayed excellent catalytic activity for several oxidative organic transformations including late-stage C–H functionalization of aldehydes with NH₂OR to valuable primary amides in nonconventional aqueous media with excellent yield. Its diverse catalytic power was established for direct oxo-scissoring of a wide range of alkenes to furnish aldehydes and/or ketones in high yield using a low catalyst loading in the water. Its smart catalytic activity under mild conditions was validated for dioxygenation of alkynes to highly demanding labile synthons, 1,2-diketones, and/or acids. This general and sustainable catalysis was successfully employed on sugar-based substrates to obtain the chiral amides, aldehydes, and labile 1,2-diketones. The catalyst is recovered and reused with a moderate turnover. The proposed mechanistic pathway is supported by isolation of the intermediates and their characterization. This multifaceted sustainable catalysis is a unique tool, especially for late-stage functionalization, to furnish the targeted compounds through frequently used amidation and oxygenation processes in the academia and industry.