Intramolecular Diels-Alder – Regioselectivity reversal


Click the structures and reaction arrows in sequence to view the 3D models and animations respectively

The usual regioselectivity may be compromised in intramolecular reactions. In some cases, it is impossible for the reagents to get together in the ‘correct’ orientation. The ester (methyl-2,7,9-decatrienoate) above has a short chain of carbons between its diene and dieneophile. This restricts the orientation and produces an endo transition state which leads to a trans ring fusion.

G. Brieger and J. N. Bennett, Chem. Rev., 1980, 80, 63–97.



Provided by the