773892-46-9Relevant academic research and scientific papers
Combined computational and experimental studies of the mechanism and scope of the retro-Nazarov reaction
Harmata, Michael,Schreiner, Peter R.,Lee, Dong Reyoul,Kirchhoefer, Patrick L.
, p. 10954 - 10957 (2007/10/03)
Density functional theory calculations (B3LYP/6-31+G*) demonstrate that conjugating and electron-donating substituents at carbons three and four of a cyclopentenyl oxyallylic cation should have a rate-accelerating effect on the retro-Nazarov reactions of these species. The retro-Nazarov reaction of these intermediates is predicted to exhibit significant torquoselectivity when carbon three is substituted with a methoxy and a methyl group. Experimental studies show that oxyallylic cations can undergo effective retro-Nazarov reactions when two alkyl and one aryl/vinyl groups are on carbons three and four. An equal number of alkyl substituents or a single aryl substituent is not effective in promoting the reaction. Interestingly, a single alkoxy substituent at carbon three is sufficient for the retro-Nazarov reaction to occur. The methodology developed was used in a total synthesis of the natural product turmerone.
