New Chemistry of Sulfur Containing Molecules: Part1: Brook Rearrangement Mediated Synthesis of Disubstituted Thiophenes, Part 2: Application of S-Nitrosation in Organic Synthesis
Devarie Baez, Nelmi Omar
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Sulfur atoms are contained in a variety of functional groups across many organic molecules. Most of these functional groups are very interesting synthetic targets because of their significance in many research fields including pharmaceutical, materials science, and chemical biology. For instance, the thiophene scaffold is one of the most targeted molecules within sulfur functionalities. This organic functionality has demonstrated many challenges regarding chemical manipulation and reaction efficiency. In the first part of the dissertation the intent is to address carbon functionalization of thiophene substrates by means of Brook rearrangement. To highlight the potential, versatility, and significance of Brook rearrangement in multicomponent strategies, a review will be provided in chapter 1. Chapters 2 and 3, will demonstrate synthetic equivalents of certain thiophenes substrates, such as dianion or cation-anion synthons, and their application for the functionalization of the thiophene ring at C-2 and C-3 positions. The second part of the dissertation focuses on another class of sulfur containing molecules, S-nitrosothiols and thioacids. In particular, S-nitrosothiol compounds are of valuable importance in biological chemistry, but somehow are ignored as organic synthons due to their instability. However, under some conditions their reactivity is controllable and undergoes interesting functional group interchange. In chapter 4, a review that entails the current status of this field, particularly the chemistry and applications of S-nitrosothiols in organic synthesis, is described. A recent example in this field is discussed in chapter 5, with the synthesis of 3-substituted benzisothiazoles. The strategy features S-nitrosation of o-mercaptoacylphenone derivatives and phosphine mediated Wittig type reactions to furnish the title compounds. In addition, chapter 6 discusses some preliminary results that demonstrate the capability of C-nitroso compounds to activate thioacids substrates and its' application in amide synthesis.