The origin of endo stereoselectivity in the hetero-Diels-Alder reactions of aldehydes with ortho-xylylenes: CH-π,π-π, and steric effects on stereoselectivity Journal Article
| Authors: | Ujaque, G.; Lee, P. S.; Houk, K. N.; Hentemann, M. F.; Danishefsky, S. J. |
| Article Title: | The origin of endo stereoselectivity in the hetero-Diels-Alder reactions of aldehydes with ortho-xylylenes: CH-π,π-π, and steric effects on stereoselectivity |
| Abstract: | Theoretical studies of stereoselectivity have been carried out with B3LYP and MP2 calculations. The high endo selectivity of hetero-Diels-Alder reactions of ortho-xylylenes with acetaldehydes is shown to result from attractive CH-π interactions between alkyl groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the hetero-Diels-Alder reactions of orthoxylylenes with benzaldehyde, the stereoselectivity is shown to be mainly governed by the attractive π-π interactions between the phenyl rings of the benzaldehyde and the ortho-xylylene. MP2 calculations are necessary to reproduce the stabilizing dispersion interactions. |
| Keywords: | models, molecular; molecular interaction; chemical reactions; theoretical model; aldehydes; reaction analysis; molecular conformation; stereochemistry; stereoisomerism; calculation; cycloaddition; molecular stability; aldehyde; xylenes; stereoselectivity; dispersions; acetaldehyde; article; ab initio calculations; pi interactions; stacking interactions; endo stereoselectivity; hetero-diels-alder reactions; ortho xylene; phenyl group |
| Journal Title: | Chemistry - A European Journal |
| Volume: | 8 |
| Issue: | 15 |
| ISSN: | 0947-6539 |
| Publisher: | Wiley V C H Verlag Gmbh |
| Date Published: | 2002-08-02 |
| Start Page: | 3423 |
| End Page: | 3430 |
| Language: | English |
| DOI: | 10.1002/1521-3765(20020802)8:15<3423::aid-chem3423>3.0.co;2-x |
| PUBMED: | 12203322 |
| PROVIDER: | scopus |
| DOI/URL: | |
| Notes: | Export Date: 14 November 2014 -- Source: Scopus |
