The preparation and resolution of 2-(2-pyridyl)- and 2-(2-pyrazinyl)-Quinazolinap and their application in palladium-catalysed allylic substitution

The preparation and resolution of the axially chiral ligands, 2-(2-pyridyl)-and 2-(2-pyrazinyl)-Quinazolinap, is described. They were prepared as racemates in good yield in eight steps and were resolved by the separation of diastereomeric palladacycles. X-ray crystal structures of the (S,R)-palladacycles were determined and are discussed. Application in palladium-catalysed allylic alkylation of dimethyl malonate and 1,3-diphenylpropenyl acetate afforded ees up to 81%.