Isomerization Reaction of Olefin Using RuClH(CO)(PPh3)3
- 24 May 2000
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 65 (13) , 3966-3970
- https://doi.org/10.1021/jo9918753
Abstract
When methyl 5-(tert-butyldiphenylsilyl)oxy-2-pentenoate was refluxed in toluene in the presence of RuClH(CO)(PPh3)3 (5 mol %), double-bond migration took place to afford methyl 5-(tert-butyldiphenylsilyl)oxy-4-pentenoate in high yield. This means that the double bond conjugated with the ester moiety migrates to a deconjugated position by a ruthenium catalyst. We planned to prepare an enol ether from α,β-unsaturated compounds having an ether moiety in a tether using ruthenium-catalyzed isomerization of the double bond. As a result, silyl or benzyl enol ether was obtained from the α,β-unsaturated ester having alcohol protected by the silyl or benzyl group in a tether in high yield. In this reaction, double bond migration of α,β-unsaturated ketone and α,β-unsaturated amide took place to produce deconjugated compounds. Moreover, the double bond of α,β-unsaturated ester having a triple or double bond in a molecule migrated to produce conjugated enyne and diene. On the other hand, treatment of a bis-metalated compound having an α,β-unsaturated ester moiety or the double bond in a tether with RuClH(CO)(PPh3)3 gave allyl bis-metalated compound in good yield. These compounds are useful units in synthetic organic chemistry.Keywords
This publication has 27 references indexed in Scilit:
- Intramolecular Cyclizations of Enynes Using RuClH(CO)(PPh3)3The Journal of Organic Chemistry, 1998
- An Alternative, Highly Stereocontrolled Synthesis of Trisubstituted Cyclopropane Derivatives from Methyl Bis(tributylstannyl)propionateThe Journal of Organic Chemistry, 1997
- Highly Stereocontrolled Cyclopropanation by the 1,3-Elimination of a Bis(tributylstannyl)propanol DerivativeThe Journal of Organic Chemistry, 1996
- Intramolecular Allylstannane-Aldehyde Cyclizations: Stereochemical Results with Flexible Tethers for Reactions Forming VinylcyclohexanolsJournal of the American Chemical Society, 1995
- Stereochemical Studies on the Addition of Allylstannanes to Aldehydes. The SE' ComponentThe Journal of Organic Chemistry, 1994
- Reactions of RuClH(CO)(PPh3)3 with Allylic Amines: Insertions and an Unusual Carbon-Nitrogen Bond Cleavage of Allylic AminesOrganometallics, 1994
- Stereochemistry of allylmetal-aldehyde condensations. 2. AllylstannanesJournal of the American Chemical Society, 1984
- STEREOSELECTIVE ACYCLIC SYNTHESIS VIA ALLYLMETALS: AN EFFICIENT SYNTHESIS OF (±)-4-METHYLHEPTAN-3-OL, AN AGGREGATION PHEROMONE OF THE SMALLER EUROPEAN ELM BARK BEETLEChemistry Letters, 1982
- RUTHENIUM HYDRIDE-CATALYZED DOUBLE BOND MIGRATION OF 2,5-DIMETHOXY-2,5-DIHYDROFURANS. A NEW PROCESS FOR THE PREPARATION OF γ-KETOESTERSChemistry Letters, 1982
- Homogeneous catalysis of olefin isomerisation. Part V. Pent-1-ene isomerisation catalysed by solutions of RuHCl(PPh3)3 and of RuHCl(CO)(PPh3)3; variation of the isomeric composition of pent-2-ene and its attribution to steric factorsJ. Chem. Soc., Dalton Trans., 1974