Journal of Organic Chemistry 2012-10-19

Acetalization allows the photoheterolysis of the Ar-Cl bond in chlorobenzaldehydes and chloroacetophenones.

Carlotta Raviola, Stefano Protti, Davide Ravelli, Mariella Mella, Angelo Albini, Maurizio Fagnoni

Index: J. Org. Chem. 77(20) , 9094-101, (2012)

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Abstract

The nonaccessibility of phenyl cations by irradiation of electron-poor aryl chlorides was circumvented by transforming the carbonyl group of aromatic ketones or aldehydes into the corresponding 1,3-dioxolanes and the carboxyl group of benzoate ester into an orthoester functionality. This transformation allowed the heterolytic photoactivation of the Ar-Cl bond in protic media and the generation of phenyl cations. In the presence of π-bond nucleophiles, arylated products were obtained in good to excellent yields.


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