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

Manoni, Elisabetta; Mario, Daka; Mastandrea, Marco Michele; De Nisi, Assunta; Monari, Magda; Bandini, Marco

doi:10.1002/adsc.201600113

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.

Titolo:	Catalytic a-Allylation of Enones with Alcohols via [Gold(I)]- Mediated [3,3]-Sigmatropic Rearrangement of Propargylic Carboxylates
Autore/i:	MANONI, ELISABETTA; Mario, Daka; MASTANDREA, MARCO MICHELE; DE NISI, ASSUNTA; MONARI, MAGDA; BANDINI, MARCO
Autore/i Unibo:	MANONI, ELISABETTA Mario, Daka MASTANDREA, MARCO MICHELE DE NISI, ASSUNTA MONARI, MAGDA BANDINI, MARCO mostra contributor esterni nascondi contributor esterni
Anno:	2016
Rivista:	ADVANCED SYNTHESIS & CATALYSIS
Digital Object Identifier (DOI):	http://dx.doi.org/10.1002/adsc.201600113
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.
Data stato definitivo:	2020-02-22T09:25:57Z
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