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Journal Articles Science Year : 2017

Organocalcium-mediated nucleophilic alkylation of benzene

Abstract

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 p-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 degrees 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.
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Dates and versions

hal-01961155 , version 1 (19-12-2018)

Identifiers

  • HAL Id : hal-01961155 , version 1

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Michael S. Hill, Mary F. Mahon, Chiara Dinoi, Laurent Maron, Andrew S. S. Wilson. Organocalcium-mediated nucleophilic alkylation of benzene. Science, 2017, 358 (6367), pp.1168--1171. ⟨hal-01961155⟩
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