N-sulfenylations of sulfoximines/sulfonimidamides and radical reactions with sulfur-containing compounds in solution and under mechanochemical conditions

  • N-Sulfenylierungen von Sulfoximinen/Sulfonimidamiden und Radikalreaktionen mit schwefelhaltigen Verbindungen in Lösung und unter mechanochemischen Bedingungen

Kong, Deshen; Bolm, Carsten (Thesis advisor); Albrecht, Markus (Thesis advisor)

Aachen : RWTH Aachen University (2022)
Dissertation / PhD Thesis

Dissertation, RWTH Aachen University, 2022


The mechanochemical technique allows improving traditional transformations and discovering new chemical reactivity in the absence of solvent. The doctoral work focuses on sulfur chemistry in solutions and under mechanochemical conditions. Three major projects are covered in this thesis. The first project focuses on mechanochemical N-sulfenylations of sulfoximines and sulfonimidamides mediated by silver oxide with disulfides as sulfur reagents. The reactions are easy to perform and a wide range of functional groups is tolerated. Furthermore, the method is more sustainable and faster than its solution-based counterpart. The second project is regioselective chloro sulfoximidation of allenes. In solution, the reactions are catalyzed by a copper complex. Good to excellent yields are obtained for the majority of substrates. Under mechanochemical conditions, the reactions can be catalyzed by milling equipment made of stainless steel. In this text, no additional metal catalysts and ligands are required, and the products are formed in moderate to good yields. The second method can also be extended to sulfonyl iodide additions to several unsaturated hydrocarbons. The third project is thiosulfonylations of unactivated alkenes. Again, the reactions are catalyzed by milling equipment made of stainless steel. A wide range of substrates is tolerated and products are obtained in high yields. The process is solvent-free, and no additional metal catalysts are required.