Gold(I)-Catalyzed Propargyl Claisen Rearrangement
Top Cited Papers
- 18 November 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (49) , 15978-15979
- https://doi.org/10.1021/ja044602k
Abstract
Homoallenic alcohols are prepared from propargyl vinyl ethers using a trinuclear gold(I)−oxo complex, [(Ph3PAu)3O]BF4, as a catalyst for propargyl Claisen rearrangement at room temperature. The gold(I)-catalyzed reaction is effective for a diverse collection of propargyl vinyl ethers, including substrates containing aryl and alkyl groups at the propargylic position, and hydrogen, aryl, and alkyl substituents at the alkyne terminus. Tertiary propargyl vinyl ethers can be employed in the reaction, at slightly elevated temperatures, to afford tetrasubstituted allenes. Importantly, the rearrangement of 1,2-disubstituted vinyl ethers proceeds with excellent diastereoselectivity, and the rearrangement of chiral nonracemic propargyl vinyl ethers proceeds with excellent chirality transfer to furnish enantioenriched allenes.Keywords
This publication has 35 references indexed in Scilit:
- Gold(I)-Catalyzed Conia-Ene Reaction of β-Ketoesters with AlkynesJournal of the American Chemical Society, 2004
- A Mild C−O Bond Formation Catalyzed by a Rhenium-Oxo ComplexJournal of the American Chemical Society, 2003
- Optically Active Allenes from β-Lactone Templates: Asymmetric Total Synthesis of (−)-MalyngolideJournal of the American Chemical Society, 2000
- Tandem Enyne Allene−Radical Cyclization: Low-Temperature Approaches to Benz[e]indene and Indene CompoundsThe Journal of Organic Chemistry, 1997
- Stereochemistry of the thermal acetylenic Cope rearrangement. Experimental test for a 1,4-cyclohexenediyl as a mechanistic intermediateJournal of the American Chemical Society, 1990
- DIASTEREOSELECTIVE SYNTHESIS OF 2-HYDROXY-3,4-ALKADIENOIC ACIDS BY THE ESTER ENOLATE CLAISEN REARRANGEMENT OF PROPARGYL GLYCOLATESChemistry Letters, 1985
- Catalysis of the Cope and Claisen rearrangementsChemical Reviews, 1984
- Orthoacrylate Claisen rearrangement. An approach to aliphatic .alpha.-methylene estersThe Journal of Organic Chemistry, 1980
- Über eine neuartige Synthese von β‐Ketoallenen durch Reaktion von tertiären Acetylencarbinolen mit Vinyläthern eine ergiebige methode zur darstellung des Pseudojonons und verwandter verbindungenHelvetica Chimica Acta, 1967
- 1256. Allenes. Part X. The Claisen–Cope rearrangement of propargyl vinyl systemsJournal of the Chemical Society, 1965