Diastereo- and Enantioselective Inverse-Electron-Demand Diels-Alder Cycloaddition between 2-Pyrones and Acyclic Enol
Guanghao Huang1, Régis Guillot1, Cyrille Kouklovsky1
1Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Saclay, CNRS, 15, rue Georges Clémenceau, 91405, Orsay Cedex, France.
Abstract:
A broadly applicable diastereo- and enantioselective inverse-electron-demand Diels-Alder reaction of 2-pyrones and acyclic enol ethers is reported herein. Using a copper(II)-BOX catalytic system, bridged bicyclic lactones are obtained in very high yields (up to 99 % yield) and enantioselectivities (up to 99 % ee) from diversely substituted 2-pyrones and acyclic enol ethers. Mechanistic experiments as well as DFT calculations indicate the occurrence of a stepwise mechanism. The synthetic potential of the bridged bicyclic lactones is showcased by the enantioselective synthesis of polyfunctional cyclohexenes and cyclohexadienes, as well as a carbasugar unit.
Related Concept Videos
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Cycloaddition Reactions: Overview
Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction
Acid-Catalyzed Ring-Opening of Epoxides


