Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions

Brian J. Levandowski; Trevor A. Hamlin; Roger C. Helgeson; F. Matthias Bickelhaupt; K. N. Houk

doi:10.1021/acs.joc.8b00025

Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions

Brian J. Levandowski, Trevor A. Hamlin, Roger C. Helgeson, F. Matthias Bickelhaupt^*, K. N. Houk

^*Corresponding author for this work

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Abstract

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-difluoromethylene 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 heteroanalogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C₃ carbon of the triafulvene motif.

Original language	English
Pages (from-to)	3164-3170
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	83
Issue number	6
Early online date	22 Feb 2018
DOIs	https://doi.org/10.1021/acs.joc.8b00025
Publication status	Published - 16 Mar 2018

Funding

This work was supported by the National Science Foundation (NSF CHE-1361104), the National Institute of Health (NIH R01GM109078), and The Netherlands Organization for Scientific Research (NWO) through the Planetary and Exo-Planetary Science program (PEPSci) and the Dutch Astrochemistry Network (DAN). We thank the University of California, Los Angeles Institute for Digital Research and SURFsara for use of the Hoffman 2 and Cartesius computers, respectively. We also thank Dr. Ashay Patel and Dr. Pier Alexandre Champagne for helpful discussions and Prof. Claude Y. Legault for developing CYLview,21 which was used to generate images of the optimized structures.

Funders	Funder number
Dutch Astrochemistry Network
Planetary and Exo-Planetary Science program
National Science Foundation	CHE-1361104
National Institutes of Health
National Institute of General Medical Sciences	R01GM109078
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
National Science Foundation

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acs.joc.8b00025_Origins of the Endo and Exo Selectivities in Cyclopropenone Iminocyclopropene and Triafulvene DielsAlder CycloadditionsFinal published version, 2.43 MBLicence: Article 25fa Dutch Copyright Act

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title = "Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions",

abstract = "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-difluoromethylene 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 heteroanalogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C3 carbon of the triafulvene motif.",

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AU - Levandowski, Brian J.

AU - Hamlin, Trevor A.

AU - Helgeson, Roger C.

AU - Bickelhaupt, F. Matthias

AU - Houk, K. N.

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N2 - 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-difluoromethylene 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 heteroanalogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C3 carbon of the triafulvene motif.

AB - 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-difluoromethylene 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 heteroanalogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C3 carbon of the triafulvene motif.

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Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions

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