Asymmetric phosphinamine

The first successful axially chiral phosphinamine ligand in asymmetric catalysis was QUINAP 60 (Figure 8) reported by Brown in 1993 and the original synthesis has since been modified.94 The donor nitrogen atom is incorporated in an isoquinoline unit to form a six-membered chelate ring. 

Quinazolines take part in the same types of reactions as pyrimidines, but because of their additional benzene ring, the products of these reactions may have the added feature of hindered rotation. An example of this is the synthesis of 2-phenyl-Quinazolinap by Guiry and co-workers <99TA2797>. Suzuki coupling of 4-chloro-2-phenylquinazoline (115) with boronic acids 116 led to 117 (R = OMe). These intermediates were parlayed into phosphinamines 117 (R = PPh2) and then subjected to chiral resolution to produce new chiral phosphinamine ligands for asymmetric catalysis. 

Kiely, D. and Guiry, PJ. (2003) Palladium complexes of phosphinamine ligands in the intramolecular asymmetric Heck reaction. Journal of Organometallic Chemistry, 687, 546-561. Dounary, A.B., Hatanaka, K., Kodanko, J.J. et al. (2003) Catalytic asymmetric synthesis of quaternary carbons bearing two aryl substituents. Enantioselective synthesis of 3-alkyl-3-aryl... 

Kiely, D. and Guiry, P.J. (2003) Palladium complexes of phosphinamine ligands in the intramolecular asymmetric Heck reaction. J. Organomet. Chem., 687, 545-61. 

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