1,1-Binaphthyl-2,2-diyl Hydrogen Phosphate1

(S)-(+)

[35193-64-7]  · C20H13O4P  · 1,1-Binaphthyl-2,2-diyl Hydrogen Phosphate  · (MW 348.30) (R)-(-)

[39648-67-4] (±)

[50574-52-2]

(reagent for optical resolution of a variety of organic bases2 and helicenes;3 NMR shift reagent for determining the enantiomeric purity of secondary and tertiary amines;4 chiral ligand for homogeneous asymmetric catalysts5,6)

Alternate Name: BNPPA.

Physical Data: (S)-(+)-BNPPA: [a]D20 +605° (c 1.35, MeOH). (R)-(-)-BNPPA: [a]D20 -605° (c 1.35, MeOH). Decomposes without melting at ca. 300 °C.

Solubility: racemate: sol ethanol (10 g/100 mL), sol methanol (3 g/100 mL), slightly sol water and other organic solvents. Enantiomer: sol ethanol (6 g/100 mL), sol methanol (2 g/100 mL), slightly sol water and other organic solvents.

Form Supplied in: white solid; racemic and optically active BNPPA are commercially available.

Preparative Methods: racemic BNPPA is obtained by condensation of (±)-binaphthol (see (R)-1,1-Bi-2,2-naphthol) and Phosphorus Oxychloride followed by hydrolysis (eq 1).1 Racemic BNPPA can be resolved by recrystallization of its cinchonine salt.1

Chiral Ligand for Asymmetric Catalysts.

(S)-(+)- and (R)-(-)-BNPPA are efficient chiral ligands for the Pd-catalyzed hydrocarboxylation of alkenes.5 Naproxen can be obtained regioselectively in 91% ee (eq 2).

Dinuclear Rh complexes modified with optically active BNPPA catalyze asymmetric carbene reactions with moderate enantioselectivity (eqs 3 and 4).6


1. Jacques, J.; Fouquey, C. OS 1989, 67, 1.
2. (a) Jacques, J.; Fouquey, C.; Viterbo, R. TL 1971, 4617. (b) Arnold, W.; Daly, J. J.; Imhof, R.; Kyburz, E. TL 1983, 24, 343.
3. Mikes, F.; Boshart, G. CC 1978, 173.
4. Shapiro, M. J.; Archinal, A. E.; Jarema, M. A. JOC 1989, 54, 5826.
5. Alper, H.; Hamel, N. JACS 1990, 112, 2803.
6. (a) McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P. TL 1992, 33, 5983. (b) Pirrung, M. C.; Zhang, J. TL 1992, 33, 5987.

Ryoji Noyori & Kazuhiko Sato

Nagoya University, Japan



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