Facile Access to Terminal Nitroalkanes via Anti‐Markovnikov Hydronitration and Hydronitroalkylation of Alkenes Using Photoredox Catalysis

Abstract

The evolution of catalysis and functional group transfer reagents play a significant role in the development of anti‐Markovnikov alkene hydrofunctionalization reactions, facilitating the access to value‐added molecules. We herein report the first rational design of a modular intermolecular anti‐Markovnikov hydronitration of alkenes, enabling the direct synthesis of terminal nitroalkanes under visible light‐mediated photoredox catalysis. By employing the redox‐active organic nitrating reagent N‐nitrosuccinimide, the produced nitryl radicals, in the presence of an olefin and a hydrogen atom transfer (HAT) mediator, lead to an anti‐Markovnikov addition with complete regioselectivity. Furthermore, we present results demonstrating the use of this catalytic system for chain expansion via anti‐Markovnikov addition, utilizing substituted bromonitroalkanes as commercially available reagents. These transformations effectively address a gap in synthetic chemistry, enabling the direct synthesis of nitroalkanes from a variety of unactivated olefins in both complex molecules and unfunctionalized commodity chemicals.