Iodine (III)-mediated Chlorination, Bromination and Nitration of Tosylanilines, scope and theoretical sudies of the reaction mechanism

Abstract

1. In the chapter 1, general introduction, there are two topics discussed based on the research carried out in the doctoral thesis. In the first part, the background, general introduction, reactivity, and preparations of hypervalent iodine reagents, and their applications in organic synthesis specialy in C-X (X= -F, -Cl, -Br, -I) and C-N bond formation. In the second part, gold catalysts background, beginning history, reactivity of gold complexes and wide application in organic synthesis specialy in cycloisomerizations, cyclization, and migration reactions have been described. 2. In the chapter 2, we have developed gold(I) catalyzed reaction which starting material tertiary aniline was inserted into gold(I) catalyst in dry-DCE as a solvent at 60 0C for 20 h. In this reaction first cyclization was happened with indole formation and the benzyl group was migrate to 2 and 3 position of cyclized indole. In this reaction we got two product as a major and minor with the ratio 2:1 . 3. In the chapter 3, we have developed an efficient iodine(III)-based protocol for the chlorination and catalytic nitration of N-tosyl anilines as well as the proposed reaction mechanism is described. The synergistic combination of the commercially available [bis(trifluoroacetoxy)iodo]benzene (PIFA) with AlCl3 and (PhIO)n with Al(NO3)3, allowed the electrophilic introduction of the chlorine and nitro group in the N-tosyl aniline core in non-acidic conditions under a common strategy. Our DFT theoretical calculations, performed for the chlorination process, indicate this occurs through a cationic pathway in which the [Cl-PhI OTFA·AlCl3] is the chlorinating species and is formed under neutral conditions / Dipak Bhatu Patil.