Andriashvili V. Chemo- and stereoselective synthesis of sulfonylamides

The dissertation is devoted to the study of synthesis of functionalized sulfonamides, proceeded with preservation of the configuration of the starting compounds (for stereoselective syntheses) or with preservation of potentially active functional groups of the side chain (for chemoselective syntheses). Taking into account the long history of sulfonylamides and the fairly high number of methods for their synthesis, a literature study and comparison of sulfonyl chlorides and sulfonyl fluorides (as the main sources of the sulfonyl fragment) in the reactions of polyfunctional sulfur-containing substrates was conducted. It was shown that even considering the longer time since the beginning of the use of sulfonyl chlorides in organic synthesis, sulfonyl fluorides are much more desirable for chemoselective transformations. Moreover, this regularity is reproduced either for reactions with the preservation of an active sulfonyl group and for the reaction on the Sulfur atom with the preservation of potentially active side functional group. It is worth noting that for the chemoselective synthesis of sulfonamides (the most widespread type of modifications), more than 90% of the known literature sources consist of sulfonyl fluoride reactions. The main advantage of sulfonyl chlorides over sulfonyl fluorides for this reaction is demonstrated on the reactions of α,β-unsaturated sulfonyl halides exclusively – being an excellent Michael acceptor, (substituted) vinyl sulfonyl fluorides produce only the corresponding Michael addition products to a multiple bond or a double addition-substitution reaction in case of using of an excess nucleophile.