Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.
Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.
Institut de Chimie des Substances Naturelles CNRS, Université Paris-Sud , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Jonathan
J
Pous
Institut de Chimie des Substances Naturelles CNRS, Université Paris-Sud , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Thibaut
T
Courant
Équipe Molécules Fluorées et Chimie Médicinale, Laboratoire BioCIS (UMR-8076) - Faculté de Pharmacie, 5 Rue J.-B. Clément, 92296 Châtenay-Malabry Cedex, France.
Guillaume
G
Bernadat
Institut de Chimie des Substances Naturelles CNRS, Université Paris-Sud , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Bogdan I
BI
Iorga
Institut de Chimie des Substances Naturelles CNRS, Université Paris-Sud , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Florent
F
Blanchard
Institut de Chimie des Substances Naturelles CNRS, Université Paris-Sud , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France.
Géraldine
G
Masson
D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D008958:Models, Molecular; D008968:Molecular Conformation; D009603:Nitroso Compounds / Q000737:chemistry; D010756:Phosphoric Acids / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
D002219:Carbamates; D009603:Nitroso Compounds; D010756:Phosphoric Acids; C030242:phosphoric acid