organic chemistry - A few questions about the conditions of the Diels Alder Reactions

I'm attempting to extract the diels alder reaction into a generic reaction and am trying to gain a better understanding of it.

Can a conjugated diene react with another conjugated diene via the diels alder reaction? And is the reaction limited to only dienes or can it be expanded to polyenes?

Does anyone happen to have a link as to the details on hetero diels alder reactions and the structures that can undergo such reactions and limitations on chemical species that can react via this reaction.

Answer

Yes, conjugated dienes can react with other conjugated dienes in Diels-Alder reactions. A well known example of this is the dimerization of cyclopentadiene. All the standard caveats, restrictions, and other considerations still apply, namely:

1. The diene must not be rotationally locked in such a way that it cannot adopt an s-cis/synperiplanar conformation. As a logical corollary, cyclic dienes that are already locked into the correct s-cis conformation often have lower activation barriers.


2. The kinetics of the reaction are accelerated by electron-withdrawing substituents on the dienophile and electron-donating substituents on the diene.


3. The stereochemistry of the major product is highly substrate-dependent. A preference for the endo isomer exists in cases where the dienophile has unsaturated substituents. In those cases, the transition state is stabilized by an overlap of the $\pi$-electron system between said unsaturated substituents and the $\pi$ orbitals of the newly forming double-bond at the back of the diene. (Just as a side note, Carey & Sundberg refer to this as the "Alder rule" in Advanced Organic Chemistry, but I've never seen that term used anywhere else.)

In principle, there's no reason why two conjugated $\pi$-bonds of a polyene cannot react similarly, provided they satisfy the orbital symmetry and conformational requirements and the reaction kinetics are favorable. Even aromatic molecules can undergo Diels-Alder reactions under the right set of conditions (see, for example, the Diels-Alder reaction between benzene and furan via a benzyne intermediate). There are also numerous instances of well-documented Diels-Alder reactions involving heteroatomic dienophiles, alkynes as dienophiles, polymerization reactions, etc.

If you can get your hands on the aforementioned Carey & Sundberg book, they discuss the Diels-Alder reaction at length (including relatively rigorous explanations of the stereospecifity and reaction kinetics via molecular orbital theory). If you're looking for a comprehensive reference, I doubt there's anything superior to the venerable March's Advanced Organic Chemistry. There's a chapter on Diels-Alder reactions (along with virtually every other organic chemistry reaction known to science), as well as a massive list of accumulated primary literature references if further detail is required.