Murarka, Sandip2026-01-222026-01-222025-04-24Parida, Sushanta Kumar (2019).Construction of Carbon-Carbon and Carbon-Heteroatom Bonds using Diaryliodonium Salts as Aryl Transfer Reagents (Doctor's thesis). Indian Institute of Technology Jodhpurhttps://ir.iitj.ac.in/handle/123456789/250Arenes represent a fundamental structural motif in a diverse array of organic molecules, encompassing pharmaceuticals, clinical drug candidates, agrochemicals, and nctional materials. Hence, the development of novel and sustainable arylation methodologies are of gnificant importance in organic synthesis. Diaryliodonium salts being bench stable and readily available, renowned for their exceptional reactivity and facile preparation, serve as versatile aryl precursors in a wide range of organic ransformations. In this regard, we have developed a metal-free, one-pot, three-component coupling reaction incorporating diaryliodonium triflates, carbon disulfide, and both cyclic and acyclic aliphatic amines, resulting in the synthesis of biologically active S-aryl dithiocarbamates. Notably, the synthesized S-aryl dithiocarbamates are found to exhibit drug-like properties, as confirmed by in-silico analysis and cellular studies. Employing the same reaction methodology, we have also synthesized S-diarylmethane dithiocarbamates through coupling between cyclic and acyclic primary and secondary amines, carbon disulfide, and p-quinone methides. The key features of this method include its mild reaction conditions, high functional group tolerance, and scalability. Moreover, we have also devised a copper-catalyzed annulation of α,β-alkynic N-tosyl hydrazones with diaryliodonium salts to synthesize N-aryl pyrazoles. As established by control experiments, mechanistic investigations revealed that the copper catalyst is essential for this process, which involves sequential cyclization, deprotection, and arylation steps. Furthermore, we have demonstrated an organophotoredox-catalyzed allylic arylation and aryl sulfonylation of Morita-Baylis-Hillman (MBH) acetates utilizing diaryliodonium triflates. This methodology exhibits broad substrate scope, scalability, and high tolerance to diverse functional groups.XXII, 173penThesisTP00200