Binaphthyl-2,2-diyl Hydrogen Phosphate

Robert S. Coleman Srinivas Reddy Gurrala The Ohio State University, Columbus, OH, USA 

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)-l,l -Bi-2,2 -naphthol) and Phosphorus Oxychloride followed by hydrolysis (eq 1). Racemic BNPPA can be resolved by recrystallization of its cinchonine salt.  

Chiral Ligand for Asymmetric Catalysts. (5)-(+)- and (R)-(—)-BNPPA are efficient chiral ligands for the Pd-catalyzed hydrocarboxylation of alkenes. Naproxen can be obtained re-gioselectively in 91% ee (eq 2). 

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RESOLUTION (S)-l-Amino-2-(silyloxyme-thyl)pyrrolidines. 1,1 -Binaphthyl-2,2 -diyl hydrogen phosphate. r-Butyl hydroperox-ide-Diisopropyl tartrate-Titanium(IV) iso-propoxide. Di- x-carbonylhexacarbonyldi-cobalt. (2S)-(2a,3aa,4a,7a,7aa)-2,3,3a,4,5,6,7,7a-Octahydro-7,8,8-trime-thy 1-4,7-methanobenzofurane-2-ol. 

The previously published method for the liberation of the diol from the resolved 1,1 -binaphthyl-2,2 -diyl hydrogen phosphate entailed... 

Bringing together the concept of aminocatalysis and the activation mode of chiral phosphoric acids. List and co-workers introduced the concept of asymmetric counter anion directed catalysis (ACDC) and they applied this idea to the asymmetric reduction of enals 47 (Scheme 23) [ 135]. The catalytic species is formed by an achiral ammonium ion 60 and a chiral phosphate anion 59 derived from 3,3 -bis(2,4,6-triisopropylphenyl)-1,1 -binaphthyl-2,2 -diyl hydrogen phosphate 9 (TRIP). 

This reaction has been done with good enantioselectivity using 1, T-binaphthyl-2,2 -diyl hydrogen phosphate (BNPPA) as a chiral ligand.240... 

Dimethylbiphenyl-2,2 -dicarboxylic acid, l,l -binaphthyl-2,2 -diyl hydrogen phosphate, camphor-10-sulfonic acid, acenocoumarol, proglumide, Af-succinyl-1-phenylethylamine, 3,4-dihydro-4-(2-naphthyl)-1,3,6-trimethyl pyrimidine-2(lH)-one-5-carboxylic acid... 

Cooper et al. (26) determined the binding constants and the mobility characteristics for three binaphthyl derivatives with a-, / -, and y-CDs. As shown, the transient diastereomeric complexes of the enantiomers of these compounds differ from each other in their mobilities. This effect is most pronounced in the case of l,l -binaphthalene-2,2 -diyl hydrogen phosphate. The change in enantioseparation depending on the y-CD concentration could be explained well for each solute-y-CD pair based on the binding studies. 

Nagoya University, Japan 1, l -Binaphthyl-2,2 -diyl Hydrogen Phosphate... 

Because both (/ )-(-)-binaphthyl-2,2 -diyl hydrogen phosphate (BNDHP) and (-)-menthoxyacetic acid are relatively expensive, the search for a less-expensive resolving agent continued. Harris et al. reported the... 

Dirhodium Bis[(5)-(+)-l, r-binaphthyl-2,2 -diyl hydrogen phosphate] Rh2i " FlP)2 (HC03)2. 5H2O Dirhodium Tetrakis[(i )-(-)-l,l -binaphthyl-2,2 -diyl hydrogen phosphate] Rh2(/ -BNHP)4 ... 

Capillary electrophoresis (CE) features increasingly in chiral separations. The use of cyclodextrins as chiral selectors is commonplace. Micellar electro-kinetic chromatography (MEKC) was used for the chiral separation of enantiomers of l,r-binaphthyl-2,2 -diyl hydrogen phosphate. ... 

The (S) enantiomer of l,l -bis-2-naphthol (9) 2,2 -dimethoxy-l,T-binaph-thyl, and l,T-binaphthyl-2,2 -diyl hydrogen phosphate were preferentially included by heptakis(2,3,6 tri-0-methyl)-/ -CD [82]. Addition of CD to the (S)-enantiomer caused fluorescence enhancement higher than that observed for the (J )-enantiomer. Moreover, the complex between the trimethyl- -CD and (S)-9 was found to have a stoichiometry of 2 1 while the complex with (J )-g has 1 1 stoichiometry. Unsubstituted jS-CD did not give enantioselec-tive complexation. 

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