Reaction Method Study On Alfa-Ketoacylation And Aroylation Of NH-Sulfoximines

The oxidative coupling methodologies through the C-H activation pathway are of great importance for the formation of C-C bonds and C-X bonds in organic chemistry. In the past decades, the oxidative protocols have aroused extensive research interests for being unique and effective tools towards some important organic molecules and natural products in organic synthetic chemistry.Sulfoximine is an important constructive unit in many drugs exhibiting some special biological activities. The sulfoximine chemistry has drawn widespread attention due to the broad existence in some important intermediates for preparations of pesticide and medicine. Thus it is highly desired for the synthesis of some sulfoximine derivatives. Therefore, some protocols for the formation of C-N bond were turned to for the derivation of NH-sulfoximines in the pharmaceutical industry. Typically, some non-metal or transition metal catalyzed methodologies were well-demonstrated thus far for different purposes. Cross dehydrogenative coupling reactions were usually utilized for the coupling of C-N bonds due to the high atom/step economy and good sustainability.Based on the extensive literature investigations, the thesis focused on explorations of various the N-funcationalization methods from NH-sulfoximine through a dual C-H/N-H activation pathway via radical intermediates.1. A highly efficient synthetic method for the preparation of a-ketoacyl sulfoximines has been developed. A series of desired 2-oxo-2-arylacetyl sulfoximines were successfully synthesized in good to excellent yields (up to 93% yield). The unprecedented protocol required no extra solvents, bases, or additives and demonstrates outstanding compatibility with assorted functional groups (up to 27 examples). Meanwhile this research studies the reaction temperature, catalyst, quantity of catalyst, oxidant and its quantity, solvent, reaction time and proposed a plausible mechanism. With the optimal conditions, twenty sevens N-aroylated sulfoximines derivatives were ultimately synthesized with structural elucidations by NMR?IR?MS and HRMS. Moreover, it illustrated a noval and a practical straightforward route to a variety of a-ketoacyl sulfoximines under the solvent-free conditions from simple and readily available starting materials.2. A novel protocol towards N-aroylated sulfoximines from NH-sulfoximines and methyl arenes was herein demonstrated. In the presence of elemental I2 and tert-butyl hydroperoxide (TBHP), the direct oxidative coupling reactions of methyl arenes and NH-sulfoximines proceeded smoothly under metal-free and solvent-free conditions to generate the corresponding products in good yields (up to 94% yield). Meanwhile this research studies the reaction temperature, catalyst, quantity of the catalyst, oxidants and its quantity, base, quantity of base, solvent, time and proposed a possible mechanism. Under the optimal conditions, thirty five N-aroylated sulfoximine derivatives were ultimately synthesized with structural elucidations by NMR?IR?MS and HRMS. Moreover, it illustrated a practical straightforward route to a variety of N-aroylated sulfoximines under metal-free conditions from simple and readily available starting materials.