Photocatalytic Anti-Markovnikov Radical Hydro- and Aminooxygenation of Unactivated Alkenes Tuned by Ketoxime Carbonates

A tunable photocatalytic method is reported for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes using readily accessible ketoxime carbonates as the diverse functionalization reagents. Mechanistic studies reveal that this reaction is initiated through an energy-transfer-promoted N-O bond homolysis of ketoxime carbonates leading to alkoxylcarbonyloxyl and iminyl radicals under visible-light photocatalysis, followed by the addition of alkoxylcarbonyloxyl radical to alkenes. By taking advantage of the different stability of the iminyl radicals, the generated carbon radical either abstracts a hydrogen atom from the media to form the anti-Markovnikov hydrooxygenation product, or it is trapped by the persistent iminyl radical to furnish the aminooxygenation product. Notably, this is the first example of direct hydrooxygenation of unactivated olefins with anti-Markovnikov regioselectivity involving an oxygen-centered radical.

Automated summary

A tunable photocatalytic method using ketoxime carbonates as reagents has been developed for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes. The reaction is initiated by N-O bond homolysis of ketoxime carbonates under visible-light photocatalysis, followed by generation of alkoxylcarbonyloxyl and iminyl radicals leading to carbon radical addition to alkenes. The carbon radical can either abstract a hydrogen atom to form hydrooxygenation product or be trapped by iminyl radical to yield aminooxygenation product.