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.