Details

Autor(en) / Beteiligte

• Wilson, Andrew S. S.
• Hill, Michael S.
• Mahon, Mary F.
• Dinoi, Chiara
• Maron, Laurent

Titel

Organocalcium-mediated nucleophilic alkylation of benzene

Ist Teil von

• Science (American Association for the Advancement of Science), 2017-12, Vol.358 (6367), p.1168-1171

Ort / Verlag

United States: American Association for the Advancement of Science

Erscheinungsjahr

2017

Quelle

American Association for the Advancement of Science

Beschreibungen/Notizen

• The electrophilic aromatic substitution of a C–H bond of benzene is one of the archetypal transformations of organic chemistry. In contrast, the electron-rich π-system of benzene is highly resistant to reactions with electron-rich and negatively charged organic nucleophiles. Here, we report that this previously insurmountable electronic repulsion may be overcome through the use of sufficiently potent organocalcium nucleophiles. Calcium n-alkyl derivatives—synthesized by reaction of ethene, but-1-ene, and hex-1-ene with a dimeric calcium hydride—react with protio and deutero benzene at 60°C through nucleophilic substitution of an aromatic C–D/H bond. These reactions produce the n-alkyl benzenes with regeneration of the calcium hydride. Density functional theory calculations implicate an unstabilized Meisenheimer complex in the C–H activation transition state.