Aryl versus Alkyl Redox-Active Diazoacetates ─ Light-Induced C-H Insertion or 1,2-Rearrangement

Abstract

Diazo compounds with redox-active leaving groups are versatile reagents for orthogonal functionalizations, previously utilized in the Rh-catalyzed synthesis of highly substituted cyclopropanes. Photochemical activation of aryl-substituted diazoacetates generates carbenes, whereas redox-active esters can furnish C-radicals via the photoexcitation of EDA complexes. However, the photochemical behavior of these two functionalities, while present in one molecule, remains to be defined. We demonstrate that under light irradiation, reactions occur only on the diazo moiety, leaving the NHPI functionality intact. Not only aryl- but also alkyl-substituted NHPI diazoacetates are activated by blue light; either C-H insertion or the hydrogen/carbon 1,2-rearrangement occurs depending on the aryl/alkyl group.