Dirhodium(II)-Catalyzed Sulfide Oxygenations: Catalyst Removal by Coprecipitation with Sulfoxides

作者：Zhao, Lili; Zhang, Hongyang; Wang, Yuanhua^*

来源：Journal of Organic Chemistry, 2016, 81(1): 129-136.

DOI：10.1021/acs.joc.5b02400

• TERT-BUTYL HYDROPEROXIDE
• C-H AMINATION
• DIRHODIUM CAPROLACTAMATE
• ORGANIC SULFIDES
• RECOVERABLE CATALYSTS
• COMPLEXES
• OXIDATIONS
• FUNCTIONALIZATION
• LIGANDS
• DESIGN

The dirhodium(II) carboxylate complex Rh-2(esp)(2) (esp = alpha,alpha,alpha',alpha-tetramethyl-1,3-benzenedipropanoate) was shown to catalyze the sulfoxidation of organic sulfides using tert-butyl hydroperoxide as the oxidant. Due to the unique structure of Rh-2(esp)(2) and its stable Rh-2(II,II) catalyst resting state, the rhodium catalyst is able to precipitate as a Rh-2(esp)(2)-sulfoxide complex following the reaction which makes separation of the catalyst from the products very convenient. The precipitated Rh-2(esp)(2)-sulfoxide complexes could be reused to catalyze sulfide oxygenation reactions without considerable loss of activity. Mechanistic studies suggest that the axial ligands fine-tune the redox potential of the dirhodium(II,II) compounds and determine the predominant catalyst species in the oxidation reaction.

• 出版日期2016-1-1
• 单位四川大学