Journal article

Publication year: 2004

Pages: 10954-10957

Journal: Journal of the American Chemical Society

Volume number: 126

Issue number: 35

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/ja048942h

Publisher: American Chemical Society

Abstract: 
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.

Harvard Citation style: Harmata, M., Schreiner, P., Lee, D. and Kirchhoefer, P. (2004) Combined computational and experimental studies of the mechanism and scope of the retro-Nazarov reaction, Journal of the American Chemical Society, 126(35), pp. 10954-10957. https://doi.org/10.1021/ja048942h

APA Citation style: Harmata, M., Schreiner, P., Lee, D., & Kirchhoefer, P. (2004). Combined computational and experimental studies of the mechanism and scope of the retro-Nazarov reaction. Journal of the American Chemical Society. 126(35), 10954-10957. https://doi.org/10.1021/ja048942h