Non-biaryl atropisomers in organocatalysis.
A new class of 6'-hydroxy cinchona alkaloids, with a non-biaryl atropisomeric functionalisation at position 5' of the quinoline core can be prepared by an easy amination procedure. These are the first derivatives for which the principle of atropisomerism is engrafted in the classical core of the cinchona alkaloids. The aminated cinchona alkaloids are effective organocatalysts for the Michael addition of beta-keto esters to acrolein and methyl vinyl ketone, in up to 93 % ee (ee=enantiomeric excess), as well as for the asymmetric Friedel-Crafts amination of a variety of 2-naphthols, permitting the preparation of the latter in up to 98 % ee. The aminated 8-amino-2-naphthol itself is the first chiral organocatalyst based on non-biaryl atropisomerism. The two enantiomers of this chiral primary amine can be used for the direct alpha-fluorination of alpha-branched aldehydes. The fluorinated compounds can thereby be accessed in up to 90 % ee.
Brandes
Sebastian
S
The Danish National Research Foundation, Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark.
Niess
Barbara
B
Bella
Marco
M
Prieto
Auxiliadora
A
Overgaard
Jacob
J
Jørgensen
Karl Anker
KA