Catalytic -Allylation of Enones with Alcohols via [Gold(I)]-Mediated [3,3]-Sigmatropic Rearrangement of Propargylic Carboxylates
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- 作者：Elisabetta Manoni ; Mario Daka ; Marco M. Mastandrea ; Assunta De Nisi ; Magda Monari and Marco Bandini
- 关键词：alcohols ; allylation ; enones ; gold catalysis ; rearrangement
- 刊名：Advanced Synthesis & Catalysis
- 出版年：2016
- 出版时间：April 28, 2016
- 年：2016
- 卷：358
- 期：9
- 页码：1404-1409
- 全文大小：719K
- ISSN：1615-4169
文摘
The site-selective -allylic alkylation of enones with alcohols <em>viaem> gold-triggered formation of nucleophilic allenoates by means of [3,3]-sigmatropic rearrangements of propargylic carboxylates is reported. A range of -alkylated enones is obtained in high yields in the presence of the gold complex [JohnPhosAu(ACN)]SbF6 (2 mol%) as the promoting agent. Examples of allylation/Friedel–Crafts alkylation sequences are also provided, delivering densely functionalized dihydroindenes and dihydrobenzo[7]annulenes in a one-pot procedure in moderate yields. The role of the Brønsted acidity (i.e., pivalic acid) delivered during the reaction course in assisting the formation of carbocationic intermediates is documented.