Transition Metal-Catalyzed Synthesis of Anhydrides, Ketones, Esters and 2HBenzotriazoles via C−H Bond Functionalization

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Transition Metal-Catalyzed Synthesis of Anhydrides, Ketones, Esters and 2HBenzotriazoles via C−H Bond Functionalization During the past several decades, the field of C−H functionalization has flourished the synthetic organic chemistry. An extensive investigation of metal-catalyzed transformation of inert C−H bond to C−C and C−X (X = heteroatoms) bonds unlocks the golden opportunities in the synthesis of small molecules. Compared to classical cross-coupling reactions, the exploitation of C−H bond as one of the coupling partner would be greener and advantageous in terms of reduced waste generation, operational simplicity, avoidance of preparation of starting materials and shorten synthetic route. As a consequence, transition metal-catalyzed C−H bond strategy has been adopted as the powerful working tool for the synthesis of various small molecules at present. The contents of this thesis have been divided into five main chapters based on the experimental results carried out during the complete course of research period. Chapter I is the introductory chapter of this thesis which presents a brief overview of transition metal-catalyzed C−H bond functionalization processes: advantages, challenges, solutions and applications of them. The remaining four chapters describe the experimental works emphasizing on palladium or copper catalyzed C−C, C−N and C−O bond forming reactions via either empoying cross dehydrogenative coupling (CDC) or substrate directed C−H bond functionalization strategies. Chapter II describes a CuO nano-catalyzed, unique CDC protocol for the synthesis of carboxylic acid anhydrides via double sp2 C−H activation of arylaldehydes using TBHP as the oxidant. Chapter III demonstrates a Pd(II)-catalyzed unprecedented protocol for the ketone synthesis using terminal aryl alkenes and alkynes as new aroyl surrogates via a substrate directed sp2 C−H functionalization. Chapter IV illustrates the use of benzylic ethers as the alternative source of arylcarboxy surrogates for ester synthesis via a copper-catalyzed substrate directed sp2 C−H functionalization of 2-phenylpyridine derivatives. Chapter V describes a palladium-catalyzed elegant protocol for the synthesis of 2-aryl- 2H-benzotriazoles from azoarenes using TMSN3 as the nitrogen source and TBHP as the oxidant through substrate directed C−H functionalization strategies.
Supervisor : Bhisma K. Patel