Asymmetric copper-catalyzed Diels–Alder reaction revisited: control of the structure of bis(oxazoline) ligands

Abstract

To cite this version:Paul Le Maux, Vincent Dorcet, Gérard Simonneaux. Asymmetric copper-catalyzed Diels-Alder reaction revisited: control of the structure of bis(oxazoline) ligands. Tetrahedron, Elsevier, 2013, 69 (38) AbstractSynthesis of 1,4-bis(oxazoline) ligands bearing a bicyclo[2,2,2]backbone derived from 9,10-dihydro-9,10-ethanoanthacene trans-dicarboxylic acid was revisited. Starting from L-or D-amino alcohols and either (S,S) or (R,R)-dihydroethano trans-dicarboxylic acid, a complete series of ligands was evaluated in the copper-catalyzed Diels-Alder reaction. The most efficient ligands with a phenyl substituent on the oxazoline ring afforded enantiomeric excess up to 98%. This is different from previous results indicating that the best enantioselectivity involved a diastereomeric ligand with the meso-backbone.

Importance of C*–H Based Modes and Large Amplitude Motion Effects in Vibrational Circular Dichroism Spectra: The Case of the Chiral Adduct of Dimethyl Fumarate and Anthracene

“…Of course we are confident that this basic study will also be appreciated outside fundamental science, because it is known that anthracene adducts are precursors of compounds widely used in different fields, such as medicinal chemistry, , stereoselective synthesis, , and material science …”

“…Of course we are confident that this basic study will also be appreciated outside fundamental science, because it is known that anthracene adducts are precursors of compounds widely used in different fields, such as medicinal chemistry, 28,29 stereoselective synthesis, 29,30 and material science. 31 See section SI-1, part (a) in the Supporting Information material for description of preparation and characterization of synthesized molecules and deuterated products.…”

Metal Promoted Diels-Alder Reactions

“…The stereochemistry of both the scaffold and the chiral oxazolines can have an influence on the selectivity of the cycloaddition. The study by Le Maux et al shows that maximum enantiomeric excess is obtained with the (11S,12S)-Bis[(4'R)phenyloxazoline]-9,10-dihydro-9,10-ethanoanthracene 160 (or its enantiomer) (Scheme 49) [94]. The other diastereoisomer only leads to reduced selectivity.…”