The preparations and reactions of a-metallated enol ethers
The preparations and reactions of a-metallated enol ethers
The copper (I) catalysed coupling of α-metallated cyclic enol ethers with organolithium of Grignard reagents resulting in the stereoselective synthesis of an alkenylmetallic species is described. The reaction tolerates a wide range of organolithium or Grignard reagents, but it is unsuccessful when the process is applied to acyclic α-metallated enol ethers. Extension of this process to encompass the loss of halogen or sulphur nucleofuges in place of alkoxy groups was attempted when organolithium reagents were used as coupling partners. Two alternative routes to α-metallated enol ethers rather than by direct deprotonation have also been investigated. The first transforms 6 or 7 membered ring lactones into the corresponding α-stannylated enol ether via the enol triflate and is applicable in cases where direct metallation fails. A novel approach to acyclic α-metallated enol ethers via metallometallation of alkoxyacetlyenes through either stannylcupration or palladium-catalysed silylstannylation and stannylstannylation is reported.
University of Southampton
Barber, Christopher Gordon
1991
Barber, Christopher Gordon
Barber, Christopher Gordon
(1991)
The preparations and reactions of a-metallated enol ethers.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The copper (I) catalysed coupling of α-metallated cyclic enol ethers with organolithium of Grignard reagents resulting in the stereoselective synthesis of an alkenylmetallic species is described. The reaction tolerates a wide range of organolithium or Grignard reagents, but it is unsuccessful when the process is applied to acyclic α-metallated enol ethers. Extension of this process to encompass the loss of halogen or sulphur nucleofuges in place of alkoxy groups was attempted when organolithium reagents were used as coupling partners. Two alternative routes to α-metallated enol ethers rather than by direct deprotonation have also been investigated. The first transforms 6 or 7 membered ring lactones into the corresponding α-stannylated enol ether via the enol triflate and is applicable in cases where direct metallation fails. A novel approach to acyclic α-metallated enol ethers via metallometallation of alkoxyacetlyenes through either stannylcupration or palladium-catalysed silylstannylation and stannylstannylation is reported.
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Published date: 1991
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Local EPrints ID: 461049
URI: http://eprints.soton.ac.uk/id/eprint/461049
PURE UUID: 8f131b63-c98c-4f5c-a44c-4c0c8b0a9862
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Date deposited: 04 Jul 2022 18:34
Last modified: 04 Jul 2022 18:34
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Author:
Christopher Gordon Barber
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