Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 83, Issue 6, Pages 3164-3170Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.8b00025
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Funding
- National Science Foundation [NSF CHE-1361104]
- National Institute of Health [NIH R01GM109078]
- Netherlands Organization for Scientific Research (NWO) through the Planetary and Exo-Planetary Science program (PEPSci)
- Dutch Astrochemistry Network (DAN)
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM109078] Funding Source: NIH RePORTER
- Direct For Mathematical & Physical Scien [1361104] Funding Source: National Science Foundation
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The endo and exo stereoselectivities of Diels-Alder reactions of cyclopropenone, iminocyclopropene, and substituted triafulvenes with butadiene were rationalized using density functional theory calculations. When cyclopropenone is the dienophile, there is a 1.8 kcal/mol preference for the exo cycloaddition with butadiene, while the reaction of 3-difluoro-methylene triafulvene with butadiene favors the endo cycloaddition by 2.8 kcal/mol. The influence of charge transfer and secondary orbital interactions on the stereoselectivity of Diels-Alder reactions involving triafulvenes and hetero-analogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C-3 carbon of the triafulvene motif.
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