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Chemo‑, Regio- and Stereoselective Heck Arylation of Allylated Malonates: Mechanistic Insights by ESI-MS and Synthetic Application toward 5‑Arylmethyl-γ-lactones

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journal contribution
posted on 03.10.2014, 00:00 by Caio C. Oliveira, Marcelo V. Marques, Marla N. Godoi, Thaís Regiani, Vanessa G. Santos, Emerson A. F. dos Santos, Marcos N. Eberlin, Marcus M. Sá, Carlos R. D. Correia
We describe herein a general method for the controlled Heck arylation of allylated malonates. Both electron-rich and electron-poor aryldiazonium salts were readily employed as the aryl-transfer agents in good yields and in high chemo-, regio-, and stereoselectivity without formation of decarboxylated byproducts. Reaction monitoring via ESI-MS was used to support the formation of chelated Pd species through the catalytic cycle. Additionally, some Heck adducts were successfully used in the total synthesis of pharmacologically active γ-lactones.