Novel binaphthyl and biphenyl α- and β-amino acids and esters: Organocatalysis of asymmetric Diels-Alder reactions. A combined synthetic and computational study

Philip C. Bulman Page, Francesca S. Kinsey, Yohan Chan, Ian R. Strutt, Alexandra M.Z. Slawin, Garth A. Jones

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

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 languageEnglish
Pages (from-to)7400-7416
Number of pages17
JournalOrganic and Biomolecular Chemistry
Volume16
Issue number40
DOIs
Publication statusPublished - Oct 2018

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