Transition‐Metal‐Free Intermolecular Hydrocarbonation of Styrenes Mediated by NaH/1,10‐Phenanthroline

A transition‐metal‐free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10‐phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti‐Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH‐mediated reduction of 1,10‐phenanthroline works as an electron donor and a hydrogen source. A transition‐metal‐free intermolecular coupling strategy was developed, comprising the reaction of halocompounds with styrenes in the presence of NaH and 1,10‐phenanthroline, to afford hydrocarbonated products with complete anti‐Markovnikov selectivity. The developed strategy can be applied to a wide range of halocompounds, including aryl and alkyl halides, and shows good functional group tolerance.