Abstract
Asymmetric catalysis of the Diels-Alder reaction between cyclopentadiene and cinnamaldehydes has been studied using as catalysts a range of novel α- and β-aminoacids and aminoesters with binaphthyl and biphenyl backbones, providing enantioselectivities of up to 62% ee. B3LYP/6-31G* calculations, including free energy corrections, have been carried out on a binaphthyl catalyst example to identify transition state structures and to aid in the identification of major enantiomers. The calculated product ratios agree well with the experimental data; the transition states identified involve preferential approach of cyclopentene along a trajectory adjacent to the acid/ester group. The four lowest energy transition states display a stabilizing dipolar interaction between the carbonyl group oxygen atom and a terminal proton of the diene unit.
Original language | English |
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Pages (from-to) | 7400-7416 |
Number of pages | 17 |
Journal | Organic and Biomolecular Chemistry |
Volume | 16 |
Issue number | 40 |
Early online date | 17 Sept 2018 |
DOIs | |
Publication status | Published - 28 Oct 2018 |
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Dive into the research topics of 'Novel binaphthyl and biphenyl α- and β-amino acids and esters: organocatalysis of asymmetric Diels-Alder reactions. A combined synthetic and computational study'. Together they form a unique fingerprint.Datasets
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Novel binaphthyl and biphenyl α- and β-amino acids and esters: organocatalysis of asymmetric Diels-Alder reactions. A combined synthetic and computational study (dataset)
Bulman Page, P. C. (Creator), Kinsey, F. S. (Creator), Chan, Y. (Creator), Strutt, I. R. (Creator), Slawin, A. M. Z. (Creator) & Jones, G. A. (Creator), Cambridge Crystallographic Data Centre, 25 Jul 2018
https://dx.doi.org/10.5517/ccdc.csd.cc1yy78d and 3 more links, https://dx.doi.org/10.5517/ccdc.csd.cc1yy79f, https://dx.doi.org/10.5517/ccdc.csd.cc1yy77c, https://dx.doi.org/10.5517/ccdc.csd.cc1yy76b (show fewer)
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