Diels-Alder reactions 4-dimethylaminopyridine

The first addition of a fully aromatic pyridine, as opposed to a 2-pyridone, across the 2,5-positions, which might be a concerted Diels-Alder reaction, takes place between the bis-dimethylaminopyridine (161) and DMAD at 110°. The product (163) was obtained in 67% yield and appears to be formed via 162, which undergoes a retro-Diels-... 

A methodology that constructs the ISQ core directly from pyridines using a 7t-basic tungsten complex to disrupt the aromatic stabilization of these inert heterocycles was recently reported [70]. For example, common pyridine derivatives, e.g., 2-dimethylaminopyridine, will undergo stereoselective Diels-Alder reactions with electron-deficient alkenes, e.g., acrylonitrile. 

A review of organocatalytic asymmetric 2-1-2- and 4 -1- 2-cycloaddition reactions of ketenes has been published. The domino 1,4-dipolar addition and the Diels-Alder reaction of in situ generated Huisgen 1,4-dipoles (4), from dimethyl acetylenedicarboxy-late (DMAD) and 4-dimethylaminopyridine to 3-phenylacyhdeneoxindole (5), formed complex dispirooxindole-fused heterocyclic compounds (6) (Scheme 2). A multicat-alytic one-pot Diels-Alder/benzoin reaction sequence has been developed for the synthesis of complex tetrahydrocarbazoles possessing four stereogenic centres. ... 

Scheme 6.5 Monomers synthesised via thiol-ene reaction to be used further in reversible Diels-Alder polymerisations. DCC N,N -Dicyclohexylcarbodiimide and DMAP 4-dimethylaminopyridine [17,18]...

---