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Room-Temperature Coupling/Decarboxylation Reaction of α‑Oxocarboxylates with α‑Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones

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posted on 2017-01-04, 00:00 authored by Zhen He, Xiaotian Qi, Zhijie She, Yinsong Zhao, Shiqing Li, Junbin Tang, Ge Gao, Yu Lan, Jingsong You
A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.