Disulfoxide-Palladium-catalyzed Allylic C-H Bond Directly Functionalization

During the past decade, there was more interest in the functionalization of the allylic C-H bond of alkenes. As opposed to traditional Trost-Tsuji reactions, this strategy avoids the prefunctionalization of the alkene. Many transition metals have been used to promote such processes, and palladium has proved to be one of the best catalysts as it offers great advantages from the point of view of substrate scope and selectivity. White and Shi group found that disulfoxide ligand can effectively promote palladium-catalyzed allyl C-H bond functionalization.Formation of C-O bond is one of the most fundamental transformation in organic chemistry, it has been reported by catalyzed allylic C-H bond,but the nucleophilic reagents usually is carboxylic acids (acetic acid, benzoic acid, etc.), and with a hydroxylamine compound to formate C-O bond has not been reported, in order to expand the nucleophile substrate range, we studied the reaction of allylic C-H bond with hydroxylamine compounds by disulfoxides-palladium catalyzed.Firstly, the reaction conditions were explored and found that we got an excellent yield (100%) when 1,2-bis(tert-butylsulfinyl)ethane as ligand, it is the first time that 1,2-bis(tert-butylsulfinyl)ethane as ligand to build C-O bond. The reaction conditions were optimized:dichloromethane as solvent, 1,2-bis(tert-butylsulfinyl)ethane as ligand, 1,4-benzoquinone as oxidizing agent, nucleophile N-hydroxyphthalimide and N-hydroxysuccinimide as nucleophile, mild reaction conditions. Then we explored the olefin substrate scope and obtained a series of new compounds, and then we studied the reaction mechanism and proposed mechanism of the reaction. Finally, our product was subjected to applied research.