Title: Secondary Orbital Interactions Enhance the Reactivity of Alkynes in Diels-Alder Cycloadditions
Authors: Levandowski, Brian J. 
Svatunek, Dennis  
Sohr, Barbara 
Mikula, Hannes  
Houk, K. N. 
Category: Original Research Article
Issue Date: 13-Feb-2019
Citation: 
Levandowski, B. J., Svatunek, D., Sohr, B., Mikula, H., & Houk, K. N. (2019). Secondary Orbital Interactions Enhance the Reactivity of Alkynes in Diels-Alder Cycloadditions. Journal of the American Chemical Society, 141(6), 2224–2227. https://doi.org/10.34726/2101
Journal: Journal of the American Chemical Society 
ISSN: 0002-7863
Abstract: 
We have investigated the inverse electron-demand Diels-Alder reactions of trans-cyclooctene (TCO) and endo-bicyclo[6.1.0]nonyne (BCN) with a 1,2,4,5-tetrazine, a cyclopentadienone, and an ortho-benzoquinone. Tetrazines react significantly faster with TCO compared to BCN because the highest occupied molecular orbital (HOMO) of TCO is significantly higher in energy than the HOMO of BCN and there is less distortion of the tetrazine. Despite the different HOMO energies, TCO and BCN have similar reactivities toward cyclopentadienones, while BCN is significantly more reactive than TCO in the cycloaddition with ortho-benzoquinone. We find that the higher reactivity of BCN compared to TCO with ortho-benzoquinone is due to secondary orbital interactions of the BCN HOMO-1 with the diene LUMO.
Keywords: Addition reactions; Interaction energies; Chemical reactions; reactivity; Alkyls
DOI: 10.1021/jacs.8b13088
DOI: 10.34726/2101
Organisation: E163 - Institut für Angewandte Synthesechemie 
License: In Copyright 1.0
Publication Type: Article
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