The synthesis and resolution of a new axially chiral Quinazolinap ligand are reported. The application of this and other related P-N ligands to the copper catalyzed beta-borylation of alpha,beta-unsaturated esters resulted in conversions of up to 100% and ee values of up to 79%. A diastereomerically pure palladacycle of the new ligand was characterised by X-ray crystallography.
The synthesis of four new members of the Quinazolinap series of ligands is described. Three of these ligands were prepared by post-resolution modification of the known ligand (R)-7-chloro-2-isopropyl-Quinazolinap, a new approach which offers an expedient route to a range of enantiopure ligands as it precludes the need for resolution of each ligand prepared. The remaining ligand, 7-chloro-2-methylQuinazolinap, was prepared in a seven-step synthetic sequence incorporating palladium-and nickel-catalyzed transformations as the key steps. A diastereomerically pure palla-
Organo-boron compounds S 0040 Axially Chiral P-N Ligands for the Copper Catalyzed β-Borylation of α,β-Unsaturated Esters. -New catalysts of type (I) and (II) are synthesized and applied to the title reaction. -(FLEMING, W. J.; MUELLER-BUNZ, H.; LILLO, V.; FERNANDEZ, E.; GUIRY*, P. J.; Org. Biomol. Chem. 7 (2009) 12, 2520-2524; Cent. Synth. Chem. Biol., Univ. Coll., Belfield, Dublin, Ire.; Eng.) -Y. Steudel 45-169
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