ASYMMETRIC CARBON-CARBON-BOND-FORMING REACTIONS CATALYZED BY BIFUNCTIONAL CINCHONA ALKALOIDS

摘要

One aspect of the present invention relates to quinine-based and quinidine-based catalysts. In certain embodiments, the quinine-based and quinidine-based catalysts contain a hydroxy group at the 6' position. In certain embodiments, the quinine-based and quinidine-based catalysts contain an O-aryl group or an O-aroyl group at the CP position. In certain embodiments, the quinine-based and quinidine-based catalysts contain an optionally substituted O-diazene group or an optionally substituted O-benzoyl group at the CP position. In certain embodiments, the quinine-based and quinidine-based catalysts contain a thiourea at the CP position, hi certain embodiments, the quinine-based and quinidine-based catalysts contain an NH(=S)NH-aryl group at the CP position. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or prochiral imine, comprising the step of: reacting a prochiral alkene or imine with a nucleophile in the presence of a catalyst; thereby producing a chiral, non-racemic compound; wherein said catalyst is a derivatized quinine or quinidine. In certain embodiments, the nucleophile is a malonate or ß-ketoester. Li certain embodiments the nucleophile is an alkyl or aryl or aralkyl 2-cyano-2-alkylacetate. In certain embodiments the nucleophile is an alkyl or aryl or aralkyl 2-cyano-2-arylacetate. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of: reacting a racemic aldehyde or racemic ketone with a nucleophile in the presence of a derivatized quinine or quinidine, thereby producing a non-racemic, chiral compound. In certain embodiments, the kinetic resolution is dynamic.