Chiral compounds 2,2 -Dihydroxy-1,1 -binaphthyl

Among the preparative methods used for obtaining P-chiral phosphorus compounds, there are procedures involving the use of optically pure auxiliaries like (—)-menthol [40], (—)-ephedrin [41,42], or more recently, the kinetic resolution of 1-hydroxymethylalkylphenylphosphine oxides using Pseudomonas or Candida antarctica lipases [43], It has been found that some [(alkyl-substituted)arene] phosphinates and phosphine oxides can also be resolved efficiently by inclusion complexation with optically active 2,2 -dihydroxy-1, 1 -binaphthyl (17) [44],... 

Toda, F., and Tanaka, K. (1997) New Chiral Ammonium Salt Hosts Derived from Amino Acids Very Efficient Optical Resolution of 2,2 -Dihydroxy-l,r-binaphthyl by Complexation with These Host Compounds, Chem. Commun., 1087-1088. 

The reagent (7 )- or (S)-BINAL-H (7), developed by Noyori, is undoubtedly the most useful LAH complex reported so far for the asymmetric reduction of a variety of carbonyl compounds." The reagent is prepared from (R)- or (S)-2,2 -dihydroxy-1,T-binaphthyl (3) (BINAL). Both enantiomers of BINAL are commercially available, although they are somewhat expensive. The chiral ligand, however, can be recovered after the reduction and reused. Equimolar quantities of BINAL and LAH are initially mixed together to form a LAH complex that has a C2 axis of sym-... 

In 1951 Bothner-By first attempted asymmetric reductions based on the conversion of lithium aluminum hydride (LAH) into a chiral alkoxy derivative by reaction with (+)-camphor. Since this pioneering work, the use of chirally modified LAH reagents has been the focus of much attention. In 1979, the first virtually complete enantiofacial recognition of prochiral carbonyl compounds was accomplished by using LAH modified with optically pure 2,2 -dihydroxy-1,1 -binaphthyl and a simple alcohol (BINAL-H). Asymmetric reduction with chiral 2,5-dimethylborolane also gave alcohols in high optical yields." Recently, excellent results have been obtained using a chirally modified sodium borohydride... 

The well known chiral carbon skeleton designated as binaphthyl hinge has been introduced into asymmetric synthesis and resolution of racemates in the form of the derivatives of 2,2 -dihydroxy-l,r-binaphthyl (84, binaphthol). The application of chiral crown compounds containing this binaphthyl tmit for the separation of amino acids and amino acid esters by use of liquid/liquid chromatography has been described particularly by Cram et al. in detail... 

At first we tried to address the problem with Moreau s method of kinetic resolution which has been applied with great success to compounds of central chirality (ref. 18). To our knowledge this technique has not yet been used for compounds with axial chirality. To be on safe ground, we had to calibrate the effects first with compounds of similar structure and known absolute configuration. We selected 2,2 -dihydroxy-1,1 -binaphthyl (31) as an example and reacted it in the usual way with an excess of racemic 2-phenyl butanoic anhydride in the presence of pyridine. The optical excess in the remaining anhydride was determined by means of the gas chromatographic variant of Brooks and Gilbert (ref. 19) (Scheme 6). 

The absolute configuration of the chiral axis in the naturally occurring skyrin molecule has remained an outstanding question for many years. Recently, the stereochemistry of (-h) Skyrin and of atrovirin-B has been established as ( S) by making use of an extension to the Horeau method 398). Thus, reaction of each of these compounds with ( )-2-phenylbutyric anhydride led to an excess of residual (-l-)-2-phe-nylbutyric acid, which was also the case when (S)-2,2 -dihydroxy-l,r-binaphthyl was used as the substrate and esterified under the same conditions. 

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