Binaphthyl phosphate

Muller has explored enantioselective C-H insertion using optically active rhodium complexes, NsN=IPh as the oxidant, and indane 7 as a test substrate (Scheme 17.8) [35]. Chiral rhodium catalysts have been described by several groups and enjoy extensive application for asymmetric reactions with diazoalkanes ]46—48]. In C-H amination experiments, Pirrung s binaphthyl phosphate-derived rhodium system was found to afford the highest enantiomeric excess (31%) of the product sulfonamide 8 (20equiv indane 7, 71% yield). 

Hodgson and co-workers have studied the intramolecular cascade carbonyl ylide formation-cycloaddition with chiral Rh(ii) catalysts.After screening a series of chiral Rh(ii) catalysts, high enantioselectivity was achieved in the reaction of 98 by using the Rh(ii) catalyst with binaphthyl phosphate-derived chiral ligands dirhodium(ii) tetrakis[(i )-6,6 -didodecylbinaphtholphosphate] [Rh2(i -DDBNP)4] (Equation (13)). 

Our template synthesis of knots implies that the target molecules are obtained as cationic dicopper(I) complexes. Therefore we considered the possibility of interconverting both enantiomers into a pair of diastereomeric salts [137, 138] by combining them with an optically active anion. Binaphthyl phosphate (BNP") [139] drew our attention because its chirality arises from the binaphthyl core, which is twisted. This helical structure is of the same type as that of die copper double helix, precursor of the knot. Besides, both compounds are aromatic and, thus, we could expect some potentially helpful stacking interactions [87],... 

Hydrogen transfer. Using Hantzsch ester as hydrogen source imines undergo asymmetric reduction that is catalyzed by BINOL phosphates. The 3,3 -bis(9-anthracenyl)-binaphthyl phosphate ent-lA mediates the saturation of C=N bond and semihydrogenation of a conjugated triple bond. ... 

The binaphthyl phosphate ester (127) has been proposed as a resolving agent and its absolute configuration determined. A successful resolution procedure for the O-methyl ester of t-butylphosphonothioic acid has been reported. N.m.r. will distinguish between the diastereo-isomers of (128) and between the diastereoisomeric salts of (129) with o -phenylethylamine. ... 

A novel scandium complex bearing perfluorinated binaphthyl phosphate ligand, Sc[(R)-F8BNP]3, has been synthesized and used as a catalyst for asymmetric electrophilic fluorination reactions of P-keto esters [156]. In combination with 1-fluoro-pyridinium triflate (NFPY-OTf) as a fluorinating agent, the desired a-fluoro-P-keto esters were obtained in moderate to high yields (16-94%) and enantiomeric excesses (47-88%) under mild conditions. 

In a related approach, enantioselective electrophilic fluorination of a-keto esters was catalyzed with chiral rare earth metal complexes bearing perfluorinated binaphthyl phosphate ligand, using reagent 2 as the fluorinating agent (eq 7) ... 

Results from the hrst investigation of this phenomenon are reproduced in Fig. 4, which illustrates the chiral selectivity of the enantiomers of binaphthyl phosphate (BNP) by an amino acid-based molecular micelle. This observation not only indicated that the anisotropy could actually be sensitive to chiral recognition, but led us to posit that the magnitude of the difference could be a quantitative measure of the selectivity [28]. 

Fig. 4. Fluorescence anisotropy of the enantiomers of binaphthyl phosphate in the presence of a micelle polymer. Capillary electrophoresis measurements confirmed the enantiomer with the greatest interaction also had the greatest anisotropy value (inset). Reproduced with permission from Ref. [28]. Copyright 2001, Am. Chem. Soc.

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

The binaphthyl azepinium salt 59 (TT= tris(tetrachlorobenzenediolato)phosphate(V)) and corresponding azepine 60 were developed as effective catalysts for the enantioselective epoxidation of unfunctionalised alkenes, with enantiomeric excesses up to 87% <06TA2334>. 

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... 

Nakamura and co-workers provided detailed mechanistic information for the photoinduced electron transfer from tri-1 -naphthyl phosphate and related compounds to 9,10-dicyanoanthracene yielding binaphthyls The intramolecular nature of the reaction could be established by using laser flash photolysis experiments as well as fluorescence measurements [17],... 

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. 

From product analysis, fluorescence quenching, and LFP, initially formed trinaphthyl phosphates (9" ) and dinaphthyl methylphosphonates (10 ) decompose into 1,1 -binaphthyl (Np2) and 1-naphthyl phosphate or methyl phosphate, respectively. Although it is suggested that 9 and 10" change to the intramolecular ir-dimer between two Np... 

In 1990, Alper reported high enantioselectivity of 91% ee using l,T-binaphthyl-2,2 -diylhydrogen phosphate (BNPPA) 91 for the Pd(ii)-catalyzed hydrocarboxylation of 2-vinyl-6-methoxynaphthalene. Several attempts followed that used Pd(ii) catalysts in combination with chiral phosphines 90 or Recently, Hiyama and Nozaki also recorded that... 

The general affinity of guanidinium cations for oxoanions and the spatial direction of the two NH-protons makes the bicycloguanidinium core presented in the preceding chapters also a useful building block for the design of nucleotide receptors [96]. Besides carboxylates (see Sect. 2), bis(naphthoyl) host 12a binds several phophoesters in chloroform, for example, l,r-binaphthyl-2,2 -diyl phosphate the complex of the (S)-enantiomer is shown in formula 64. Still, despite the chiral nature of 12a, no enatioselectivity was observed [97]. 

S-(+)-l,l -Binaphthyl-2,2 -diylhydrogen phosphate [35193-64-7]. They have been recrystallised from EtOH. Reflux for 3h in N NaOH is required to hydrolyse the cyclic phosphate. [TET LETT 4617 7977 24, 343 1983]. 

Figure 28. Principle of the resolution of the dicopper(I) molecular trefoil knot Cu2(K-84) +. The chiral auxiliary used is S-(+)-l,l -binaphthyl-2,2 -diyl phosphate (BNP-).

A paper reports the photo-inductive reaction of di- and tri-naphthyl phosphates in the presence of sensitized DCA to afford 1,1-binaphthyl (31). No reaction was observed with mono-1-naphthyl or di- and tri-phenyl phosphate esters.72... 

To a suspension of scandium [(R)-1,1 -binaphthyl-2,2 -diyl phosphate]3 3H20 (10.9 mg, 0.01 mmol) in dry toluene (1 ml) was successively added 1 (20.8 mg, 0.1 mmol) and 2 (31.9 mg, 0.16 mmol) under an argon atmosphere, and the mixture was stirred for 24 h at room temperature (Scheme A.2). The reaction mixture was passed through a short column of silica gel. The eluent was evaporated and the residue was purified by column chromatography on silica gel (hexane-AcOEt 4 1) to give (3 S)-l,3-diphenyl-3-diphenylmethoxyaminopropan-l-one3 (40.4mg, 99%) as colorless needles. Melting point 79.5-79.8°C. 

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