Nickel-Catalyzed Benzylic Substitution of Benzyl Esters with Malonates as a Soft Carbon Nucleophile
2019
Tsuji, Hiroaki | Hashimoto, Keisuke | Kawatsura, Motoi
The nickel-catalyzed benzylic substitution of benzyl alcohol derivatives with a soft carbon nucleophile is extremely rare compared to that with a hard carbon nucleophile. We have achieved the nickel-catalyzed benzylic substitution of benzyl esters with malonates as a soft carbon nucleophile. Primary and secondary benzyl 2,3,4,5,6-pentafluorobenzoates as well as a wide variety of malonate derivatives were well tolerated in the nickel-catalyzed reaction, providing the corresponding alkylation products in 46–86% yields (34 examples). Additionally, we propose a possible reaction mechanism that would undergo via the η¹- and η³-benzylnickel intermediates.
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