title: Synthesis of new BINAP-based aminophosphines and their ³¹P-NMR spectroscopy.
abstract: BINAP aminophosphines are prevalent N,P-bidentate, chiral ligands for asymmetric catalysis. While modification via the BINAP-nitrogen linkage is well explored and has provided a diverse body of derivatives, modification of the other substituents of the phosphorous center is another avenue in generating new congeners of this important class of chiral ligands. Herein reported are new BINAP aryl aminophosphines with electron rich or deficient substituents on the aryl rings. This scalable synthesis converted readily available starting material, (S)-BINOL, to a key intermediate (S)-NOBIN, from which the final chiral aminophosphines were prepared via a palladium-catalyzed, phosphonylation reaction. The aryl substituents are able to modify the electronic properties of the phosphorous center as indicated by the range of ³¹P-NMR shifts of these new ligands. A computational analysis was performed to linearly quantitate contributions to the ³¹P-NMR shifts from both resonance and field effects of the substituents. This correlation may be useful for designing and preparing other related aminophosphines with varying ligand properties.
authors: Department Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW 2109, Australia.
authors: Christopher
authors: C
authors: Anstiss
authors: Peter
authors: P
authors: Karuso
authors: Mark
authors: M
authors: Richardson
authors: Fei
authors: F
authors: Liu
mesh_terms: D009281:Naphthalenes / Q000737:chemistry*; D019906:Nuclear Magnetic Resonance, Biomolecular; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: C406943:BINAP, 2-naphthol; D009281:Naphthalenes; D010720:Phosphines