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

Author:
Joarder, Dripta De, Gayen, Subrata, Sarkar, Rajarshi, Bhattacharya, Rajarshi, Roy, Sima, Maiti, Dilip K.
Source:
Journal of organic chemistry 2019 v.84 no.13 pp. 8468-8480
ISSN:
1520-6904
Subject:
acids, aldehydes, alkynes, amides, carbon-hydrogen bond activation, catalysts, catalytic activity, chemical reactions, chemical structure, ketones, olefin, organic chemistry, ruthenium, water solubility
Abstract:
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.
Agid:
6496713