The site-selective a-allylic alkylation of enones with alcohols via gold-triggered formation of nucleophilic allenoates by means of [3,3]-sigma- tropic rearrangements of propargylic carboxylates is reported. A range of a-alkylated enones is obtained in high yields in the presence of the gold complex [JohnPhosAu(ACN)]SbF6 (2 mol%) as the promot- ing agent. Examples of allylation/Friedel–Crafts al- kylation sequences are also provided, delivering densely functionalized dihydroindenes and dihydro- benzo[7]annulenes in a one-pot procedure in mod- erate yields. The role of the Brønsted acidity (i.e., pivalic acid) delivered during the reaction course in assisting the formation of carbocationic intermedi- ates is documented.

Catalytic a-Allylation of Enones with Alcohols via [Gold(I)]- Mediated [3,3]-Sigmatropic Rearrangement of Propargylic Carboxylates

MANONI, ELISABETTA;MASTANDREA, MARCO MICHELE;DE NISI, ASSUNTA;MONARI, MAGDA;BANDINI, MARCO
2016

Abstract

The site-selective a-allylic alkylation of enones with alcohols via gold-triggered formation of nucleophilic allenoates by means of [3,3]-sigma- tropic rearrangements of propargylic carboxylates is reported. A range of a-alkylated enones is obtained in high yields in the presence of the gold complex [JohnPhosAu(ACN)]SbF6 (2 mol%) as the promot- ing agent. Examples of allylation/Friedel–Crafts al- kylation sequences are also provided, delivering densely functionalized dihydroindenes and dihydro- benzo[7]annulenes in a one-pot procedure in mod- erate yields. The role of the Brønsted acidity (i.e., pivalic acid) delivered during the reaction course in assisting the formation of carbocationic intermedi- ates is documented.
Elisabetta, Manoni; Mario, Daka; Marco M., Mastandrea; Assunta, De Nisi; Magda, Monari; Marco, Bandini
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11585/560686
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