Here, we see another element of stereopecificity: Diels-Alder reactions with cyclic dienes favor the formation of bicyclic structures in which substituents are in the endo position.
The endo position on a bicyclic structure refers to the position that is inside the concave shape of the larger (six-membered) ring. As you might predict, the exo position refers to the outside position.
The rate at which a Diels-Alder reaction takes place depends on electronic as well as steric factors. A particularly rapid Diels-Alder reaction takes place between cyclopentadiene and maleic anhydride.
We already know that cyclopentadiene is a good diene because of its inherent s-cis conformation. Maleic anhydride is also a very good dienophile, because the electron-withdrawing effect of the carbonyl groups causes the two alkene carbons to be electron-poor, and thus a good target for attack by the pi electrons in the diene.
In general, Diels-Alder reactions proceed fastest with electron-donating groups on the diene (eg. alkyl groups) and electron-withdrawing groups on the dienophile.
Alkynes can also serve as dienophiles in Diels-Alder reactions:
Below are just three examples of Diels-Alder reactions that have been reported in recent years:
The Diels-Alder reaction is just one example of a pericyclic reaction: this is a general term that refers to concerted rearrangements that proceed though cyclic transition states. Two well-studied intramolecular pericyclic reactions are known as the Cope rearrangement . . .
. . .and the Claisen rearrangement (when an oxygen is involved):
Notice that the both of these reactions require compounds in which two double bonds are separated by three single bonds.
Pericyclic reactions are rare in biological chemistry, but here is one example: the Claisen rearrangement catalyzed by chorismate mutase in the aromatic amino acid biosynthetic pathway.
The study of pericyclic reactions is an area of physical organic chemistry that blossomed in the mid-1960s, due mainly to the work of R.B. Woodward, Roald Hoffman, and Kenichi Fukui. The Woodward-Hoffman rules for pericyclic reactions (and a simplified version introduced by Fukui) use molecular orbital theory to explain why some pericyclic processes take place and others do not. A full discussion is beyond the scope of this text, but if you go on to study organic chemistry at the advanced undergraduate or graduate level you are sure to be introduced to this fascinating area of inquiry.
- 15.10: The Diels-Alder reaction and other pericyclic reactions. Authored by: Tim Soderberg. Provided by: University of Minnesota, Morris. Located at: https://chem.libretexts.org/Textbook_Maps/Organic_Chemistry/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)/15%3A_Electrophilic_reactions/15.10%3A_The_Diels-Alder_reaction_and_other_pericyclic_reactions. Project: Chemistry LibreTexts. License: CC BY-NC-SA: Attribution-NonCommercial-ShareAlike