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

Kanako Nozawa-Kumada; So Onuma; Kanako Ono; Tomohiro Kumagai; Yuki Iwakawa; Katsuhiko Sato; Masanori Shigeno; Yoshinori Kondo

doi:10.1002/chem.202203143

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

Chemistry. 2023 Mar 28;29(18):e202203143. doi: 10.1002/chem.202203143. Epub 2023 Feb 28.

Authors

Kanako Nozawa-Kumada¹, So Onuma¹, Kanako Ono¹, Tomohiro Kumagai¹, Yuki Iwakawa¹, Katsuhiko Sato², Masanori Shigeno¹, Yoshinori Kondo¹

Affiliations

¹ Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
² Faculty of Pharmaceutical Science, Tohoku Medical and Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai, 981-8558, Japan.

PMID: 36599804
DOI: 10.1002/chem.202203143

Abstract

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.

Keywords: carboradical; hydrocarbonation; single-electron-transfer; sodium hydride; styrenes.