2,2 -Binaphthyl-3,3 -dicarboxylic acid

Ozonation of benzo[r,s,t]pentaphene (7) followed by oxidative workup led to benzo[r,s,t]pentaphene-5,8-dione (12) (14%), phthalic acid (13) (4%), p-terphenyl-2,2, 3, 2"-tetra-carboxylic acid-2, 3 -anhydride (14) (10%), and 2-(o-car-boxyphenyl)- ,10-phenanthrenedicarboxylic acid anhydride (15) (3%), with a 56% recovery of unreacted 7, Ozonation of pentaphene (11) led to a peroxidic mixture which on oxidative workup led to 2,2 -binaphthyl-3,3 -dicarboxalde-hyde (16) (16%), 2,2 -binaphthyl-3,3 -dicarboxylic acid (17) (16%), and 13 (2%), with a 28% recovery of unreacted 11. A comparison of the reactivity to ozone of carcinogenic polycyclic aromatics benzo c]phenanthrene (1), 7,12-di-methylbenz [a] anthracene (2), 3-methylcholanthrene (3), dibenz[si,]] - (4), and dibenzlsi, ]anthracene (5), benzo Si -pyrene (6) and 7, and the noncarcinogen 11, all determined in our laboratory, leads us to conclude that there is no simple, consistent correlation between carcinogenicity, K-and L-region additivity towards ozone and the Pullmans electronic theory of carcinogenesis. 

A three-component Ugi-type reaction using A/ -alkylbenzohydrazide (instead of amine) has been catalysed by an axially chiral binaphthyl dicarboxylic acid and found to proceed with up to 93% ee with an acyclic azomethine imine. Stereoselectivity of a Ugi reaction starting from an oxanorbornenone / -amino acid, R CHO, and RNC has been improved through solvent selection. ... 

Crystal structure of 1, l -binaphthyl-8,8 -dicarboxylic acid Czugler, M., Weber, E. Unpublished result (1985)... 

Binaphthyl-2,2 -dicarboxylic acid (1). (RS)-l can be resolved with brucine, which selectively forms a salt with (R)-l that is insoluble in acetone. 

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... 

In 2007, Maruoka et al. introduced chiral dicarboxylic acids consisting of two carboxylic acid functionalities and an axially chiral binaphthyl moiety. They applied this new class of chiral Brpnsted acid catalyst to the asymmetric alkylation of diazo compounds withA-Boc imines [91]. The preparation of the dicarboxylic acid catalysts bearing aryl groups at the 3,3 -positions of the binaphthyl scaffold follows a synthetic route, which has been developed earlier in the Maruoka laboratory [92]. 

In Ught of the recent developments in thiourea, diol, and phosphoric-acid-mediated catalysis, far fewer studies have focused on the use of chiral carboxyhc acids as suitable hydrogen bond donors. To this end, Mamoka synthesized binaphthyl-derived dicarboxylic acid 49 which catalyzes the asymmetric Mannich reaction of N-Boc aryl imines and tert-diazoacetate (Scheme 5.65) [120]. The authors postulate that catalytic achvity is enhanced by the presence of an addihonal car-boxyhc acid moiety given that use of 2-napthoic acid as catalyst provided only trace amounts of product... 

Similar observations were reported for tetrachloro-2,2 -diphenyldicarboxylic acid dichloride237 and 1,1 -binaphthyl-2,2 -dicarboxylic acid dichloride239-240. 

The keto-enol equilibrium of the 1,3-diketones has been the subject of intensive studies using various physical techniques and theoretical calculations [78-80], Recently, X-ray crystal analysis of acetylacetone (83) was carried out at 110 K, and it was found that it exists as an equilibrium mixture of the two enol forms 83b and 83c [81]. Room-temperature studies show an acetylacetone molecule with the enolic H-atom centrally positioned, which can be attributed to the dynamically averaged structure 83d. Application of a crystal engineering technique showed that a 1 1 inclusion complex of83 can be formed with l,l/-binaphthyl-2,2/-dicarboxylic acid in which the enol form is stabilized by a notably short intramolecular hydrogen bond [82],... 

Kano has studied extensively the recognition of anions and zwitterions by both native and derivatized cyclodextrins [ 16]. The native (3-cyclodextrin com-plexation properties were examined with respect to binaphthyl derivatives. For both l,T-binaphthalene-2,2,-dicarboxylic acid and l,T-binaphthalene-2,2 -diol phosphate almost no chiral recognition was observed. The enantiomers of binaphthyl-2,2 -dicarboxylic acid were better distinguished using a per-O-methylated (3-cyclodextrin derivative in place of the native (3-cyclodextrin. 

As Section IV will be mostly devoted to 2,4-pentanedione, acacH, it is worthwhile to dwell on this well studied species. The rate of interconversion between the keto and the enol form of acacH is rather slow at room temperature , thus they can be simultaneously detected by NMR spectroscopy it has been observed that the lower the polarity of the solvent, the higher the percentage of the enol tautomer . Electron diffraction studies indicate that in the gas phase acacH adopts the enol configuration with a keto/enol ratio of 8/92. More recently, an X-ray analysis of acacH, carried out at 110 showed that it exists as a mixture of the two enol forms 86 and 87, with the enolic hydrogen atom equally distributed over two positions close to the oxygen atoms as in 88. It should be noted that inclusion compounds containing different host molecules show different ratios of acacH in the enol form. For example, acacH exists as a dynamically averaged 1 1 mixture of 86 and 87 in an inclusion complex with l,T-binaphthyl-2,2 -dicarboxylic acid as host , while l,l-bis( >-hydroxyphenyl)cyclohexane and (4R,5R)-trawi-4,5-bis(hydroxydiphenylmethyl)-2,2-dimethyl-l,3-dioxolane include acacH in pure enolic form. ... 

Cheng LP, Dwan AH, and Gryte CC. Wholly aromatic thermotropic liquid crystalline polyesters of 4,4 -biphenol, substituted biphenols, and l,l -binaphthyl-4,4 -diol with 3,4 -benzophenone dicarboxylic acid. J. Polym. Sci. Polym. Phys. B 1995 33 211-225. 

Binaphthyl-2-2 -dicarhoxylic acid, l,r-hinaphthyl-2, 2 -dihydrogen phosphate, and 2,2 -dihydroxy-1-l -hinaphthyl-3, 3 -dicarboxylic acid 0.04 M Carbonate, pH 9.0, with noncyclooligosaccharides UV 215-235 nm ... 

The transoid-cisoid equilibrium in crowded binaphthyl compounds generates two enantiomeric cisoid forms which may interconvert. For these compounds, CTI requires heating to proceed (i.e. AG i = 23.5 kcal mol-1 for compound 2, h/2 = 14.5 min at 50 °C). Introduction of substituents increases the barrier to rotation and hence stabilizes the chiral configuration [6]. For example, (S)-1,T-binaphthyl-2,2 -dicarboxylic acid 3 could not be racemized at 175 °C in DMF (Fig. 13.IB). Depending on substituents, racemization may be favored by steric/electro-static repulsions and CTI of dicarboxylate 4 occurs at a lower temperature (AG = 24.4 kcal mol-1 for compound 2, = 51.5 min at 50 °C). 

For the 3,3 -dimethyl derivative 8, several other methods have been developed. The racemic 3,3 -dimethy] compound can be prepared by aminomcthylation of binaphthol with subsequent conversion of the aminomethy] function to a methyl group, and resolved analogously to binaphthol via the phosphoric acid derivative15. Another possibility is the preparation [oxidation of 3-hydroxy-2-naphthoic acid with iron(III) chloride] and resolution [with (S)-leucine methyl ester] of 2,2 -dihydroxy-1,l -binaphthyl-3,3 -dicarboxylic acid (7). 

In many of the recently known host-guest situations (see above), however, both coordinative and crystal lattice forces contribute to the formation of the host-guest compound. Thus, borderline cases must be treated as complex/clathrate hybrids (Fig. 14). According to the nature of the binding, we speak of coordinatoclathrates which demonstrate a certain degree of coordinative participation but have a dominant clathrate character and of clathratocomplexes, just the other way round. The inclusion compounds of l,l -binaphthyl-2,2 -dicarboxylic acid (26a) with different OH-, NH- and CH-acidic guest molecules (cf. Sect. 3) can be quoted as typical examples... 

Dihydroxy-l,r-binaphthyl-3,3 -dicarboxylic acid, dimethyl ester, X6.6 C22Hi9BrN03... 

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