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Nickel-Catalyzed Cyanation of Benzylic and Allylic Pivalate Esters

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journal contribution
posted on 04.09.2018, 00:00 by Nicholas W. M. Michel, Alexandria D. M. Jeanneret, Hyehwang Kim, Sophie A. L. Rousseaux
A nickel-catalyzed cyanation reaction of benzylic and allylic pivalate esters is reported using an air-stable Ni­(II) precatalyst and substoichiometric quantities of Zn­(CN)2. Alkene additives were found to inhibit catalysis, suggesting that avoiding β-hydride elimination side reactions is essential for productive catalysis. An enantioenriched allylic ester undergoes enantiospecific cross-coupling to produce an enantioenriched allylic nitrile. This method was applied to an efficient synthesis of (±)-naproxen from commercially available starting materials.