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Issue 40, 2014
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The origin of exo-stereoselectivity of norbornene in hetero Diels–Alder reactions

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Abstract

In this study the exo selectivity in the hetero Diels–Alder reaction of atropisomeric 5-benzylidine-2-arylimino-3-aryl-thiazolidine-4-thiones with norbornene was investigated with computational tools. Taking into account the M/P chiral character of the o-methoxyphenyl substituted heterodienes in addition to the exo/endo selectivity, 8 different transition structures were located. Based on the direction of approach of the diene and the dienophile for each plausible path it is found that endo products are not preferred because of the large distortion of norbornene and the rather eclipsed conformations of these transition state structures. Computational results are consistent with the experimental exo/endo selectivity. The computational methodology (M06-2X/6-31+G(d)//B3LYP/6-31+G(d)) was justified by comparison of the experimental rotational barriers with the calculated ones for selected compounds.

Graphical abstract: The origin of exo-stereoselectivity of norbornene in hetero Diels–Alder reactions

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Publication details

The article was received on 12 Jun 2014, accepted on 15 Aug 2014 and first published on 15 Aug 2014


Article type: Paper
DOI: 10.1039/C4OB01217H
Citation: Org. Biomol. Chem., 2014,12, 8079-8086
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    The origin of exo-stereoselectivity of norbornene in hetero Diels–Alder reactions

    S. Agopcan Cinar, S. Ercan, S. Erol Gunal, I. Dogan and V. Aviyente, Org. Biomol. Chem., 2014, 12, 8079
    DOI: 10.1039/C4OB01217H

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