Publication 274

    1. Liu, L.; Cotelle, Y.; Bornhof, A.-B.; Besnard, C.; Sakai, N.; Matile, S. “Anion-π Catalysis of Diels-Alder Reactions” Angew. Chem. Int. Ed. 2017, 56, 13066-13069 

Among concerted cycloadditions, the Diels–Alder reaction is the grand old classic, which is usually achieved with acid catalysis. In this report, hydroxypyrones, oxa-, and thiazolones are explored because they provide access to anionic dienes. Their [4+2] cycloaddition with cyclic and acyclic dienophiles, such as maleimides and fumarates, affords bicyclic products with four new stereogenic centers. Bifunctional anion–π catalysts composed of amine bases next to the π surface of naphthalenediimides (NDIs) are shown to selectively stabilize the “open”, fully accessible anionic exo transition state on the π-acidic aromatic surface. Our results also include reactivities that are hard to access with conventional organocatalysts, such as the exo-specific and highly enantioselective Diels–Alder reaction of thiazolones and maleimides with complete suppression of the otherwise dominant Michael addition. With increasing π acidity of the anion–π catalysts, the rates, chemo-, diastereo-, and enantioselectivities increase consistently.

[open archive unige:97331 • pdf ]