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Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy
Department Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW, 2109, Australia
* Author to whom correspondence should be addressed.
Received: 16 January 2013; in revised form: 8 February 2013 / Accepted: 21 February 2013 / Published: 1 March 2013
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.
Keywords: bidentate ligands; BINAP aryl aminophosphines; substituent effects; NOBIN; MAP
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MDPI and ACS Style
Anstiss, C.; Karuso, P.; Richardson, M.; Liu, F. Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy. Molecules 2013, 18, 2788-2802.
Anstiss C, Karuso P, Richardson M, Liu F. Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy. Molecules. 2013; 18(3):2788-2802.
Anstiss, Christopher; Karuso, Peter; Richardson, Mark; Liu, Fei. 2013. "Synthesis of New BINAP-Based Aminophosphines and Their 31P-NMR Spectroscopy." Molecules 18, no. 3: 2788-2802.