UNIGE document Scientific Article
previous document  unige:97331  next document
add to browser collection

Anion-π Catalysis of Diels-Alder Reactions

Published in Angewandte Chemie: International Edition. 2017, vol. 56, no. 42, p. 13066-13069
Abstract 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.
Full text
Article (Published version) (2 MB) - document accessible for UNIGE members only Limited access to UNIGE
Article (Accepted version) (3 MB) - public document Free access
Research group Groupe Matile
(ISO format)
LIU, Le et al. Anion-π Catalysis of Diels-Alder Reactions. In: Angewandte Chemie: International Edition, 2017, vol. 56, n° 42, p. 13066-13069. doi: 10.1002/anie.201707730 https://archive-ouverte.unige.ch/unige:97331

301 hits



Deposited on : 2017-10-04

Export document
Format :
Citation style :