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Stereochemical control in the ester enolate Claisen rearrangement. 2. Chairlike vs boatlike transition-state selection
- Source :
- The Journal of Organic Chemistry. 56:3572-3582
- Publication Year :
- 1991
- Publisher :
- American Chemical Society (ACS), 1991.
-
Abstract
- The preference for chair- and boatlike transition-state geometries in the ester enolate Claisen rearrangement of straight chain, carbocyclic, and heterocyclic propanoates was investigated. A novel stereoelectronic effect in pyranoid and furanoid glycal systems leads to a significant relative stabilization of the boatlike vs the chairlike TS : . The preferred transition state in six- and five-membered carbocyclic systems is highly dependent on steric factors, as the energy difference between chair- and boatlike TS : tends to be small. With straight-chain substrates, a significant contribution of the boatlike TS : to the rearrangement product mixture is only expected in bis-donor substituted allylic esters
Details
- ISSN :
- 15206904 and 00223263
- Volume :
- 56
- Database :
- OpenAIRE
- Journal :
- The Journal of Organic Chemistry
- Accession number :
- edsair.doi...........452807663354e1a23e856af6cdc82f5b
- Full Text :
- https://doi.org/10.1021/jo00011a023