Development of Catalytic Site-Selective C-H Oxidation

Abstract

Direct C-H bond oxygenation is a strong and useful tool for the construction of oxygen functional groups. After Chen and White's pioneering works, various non-heme-type iron and manganese complexes were introduced, leading to strong development in this area. However, for this method to become a truly useful tool for synthetic organic chemistry, it is necessary to make further efforts to improve site-selectivity, and catalyst durability. Recently, we found that non-heme-type ruthenium complex cis-1 presents efficient catalysis in C(sp³ )-H oxygenation under acidic conditions. cis-1-catalysed C-H oxygenation can oxidize various substrates including highly complex natural compounds using hypervalent iodine reagents as a terminal oxidant. Moreover, the catalyst system can use almost stoichiometric water molecules as the oxygen source through reversible hydrolysis of PhI(OCOR)₂ . It is a strong tool for producing isotopic-oxygen-labelled compounds. Moreover, the environmentally friendly hydrogen peroxide can be used as a terminal oxidant under acidic conditions.

Keywords: C−H Oxygenation; Late-stage functionalization; Non-heme-type catalyst; Ruthenium catalyst; Site-selective.