ABSTRACT
The dual operation of a chemical species in synthetic chemistry is an intriguing and relatively unexplored phenomenon. The application of such a species is expected to reduce the use of multiple reaction partners and catalysts/activators. Herein, we report a simple and easy-to-use protocol for the twin application of TiO(acac)2 , as a reagent and an activator to synthesize ß-enamino ketones with amines in acetonitrile. The same early transition metal precursor when employed in N,N-dimethylformamide with the amines, resulted in the formation of the substituted amides. Both reactions were explored with various substrates to check the viability of the present protocol. Moreover, experimental studies were conducted to understand the mechanism of both reactions.
ABSTRACT
Ruthenium catalyzed C-H activation is well known for its high tolerance towards the functional group and broad applicability in organic synthesis and molecular sciences, with significant applications in pharmaceutical industries, material sciences, and polymer industry. In the last few decades, enormous progress has been observed with ruthenium-catalyzed C-H activation chemistry. Notably, the vast majority of the C-H functionalization known in the literature are intermolecular, although the intramolecular variant provides fascinating new structural facet starting from the simple molecular scaffolds. Intramolecular C-H functionalization is atom economical and step efficient, results in less formation of undesired products which is easy to purify. This has created a lot of interest in organic chemistry in developing new synthetic strategies for such functionalization. The focus of this review is to present the relatively unexplored intramolecular functionalization of C-H bonds into C-X (X=C, N, O, S) bonds utilizing versatile ruthenium catalysts, their scope, and brief mechanistic discussion.
