18531-92-5

Hydrogen-bond formation with the terminal oxygen atom is considered to be the basis of dioxygen molecule activation by cytochrome P450. In order to verify the effect of this hydrogen bond, we have undertaken the synthesis of a model complex: a binaphthyl-

The (aR,aR,aR) and (aS,aS,aS) enantiomers of a chiral macrobicyclic ligand with a bicapped tris(binaphthol) structure were synthesized. Complexation of gallium(III), chromium(III) and iron(III) centres in the chiral cavities of these two ligands yielded exclusively one octahedral configuration in each case: the (aR,aR,aR) enantiomer gave a A complex and the (aS,aS,aS) enantiomer a Δ complex. These assignments were established by CD spectroscopy for chromium and iron centres and by molecular modelling.

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The design of a new class of chiral [2]catenanes is reported. The self-assembly of [2]catenanes comprising one or two 3,3'-biotyl spacers in the π-electron-deficient component, and bis-p-phenylene-34-crown-10 (BPP34C10) as the π-electron-rich component, i

Two novel metal-organic frameworks, [Cd(Bna)(DMF)2(H 2O)2] n · nDMF (I) (Bna = 2,2′-dihydroxy-l,l′-dinaphthyl-3,3′-dicarboxylate) and [Cd(Bna)(Bipy)(DMF)2] n (II) (Bipy = 4,4′- bipyridine) have been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that complex I adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II is constructed by -Cd-Bna-Cd- zigzag chains, which are further connected by Bipy into a 2D sheet. X-ray powder diffraction and thermogravimetric analyses for I and II show that they are highly themally stable in the solid state.

A process for polymerizing β-butyrolactone is disclosed comprising contacting racemic β-butyrolactone or an enantiomer thereof with a catalyst/initiator system which comprises a rare earth metal, a chiral ligand, at least one nucleophilic ligand, optional

A simple and efficient method has been developed to resolve (±)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid [(±)-BINOL-3,3′-dicarboxylic acid] (±)-1 using inexpensive and readily accessible chiral resolving agent (1R,2R)-trans-cyclohexane-1,2-diamine 2. Enantiomers of BINOL-3,3′-dicarboxylic acid were obtained in good yields and enantiomeric purity, for example, (S)-(-)-1 was isolated in 34% yield with >99% ee and (R)-(+)-1 was obtained in 36% yield with >99% ee. The formation of diastereomeric salt A between (S)-BINOL-3,3′-dicarboxylic acid and (1R,2R)-trans-cyclohexane-1,2-diamine was ascertained by using IR, single crystal X-ray crystallography, and HRMS.

Opening of racemic styrene oxide with p-toluidine catalyzed by chiral BINOL-derived polyols proceeded regioselectively mainly with the formation of 2-phenyl-2-(p-tolylamino)- ethanol with low ee values.

The present invention relates to a method for preparing enantiomerically pure compounds 1a and 1b of the following formula 1 from racemic compound 1 of the following formula 1. [formula 1] The compounds 1a and 1b of the above formula 1 respectively are im

Three novel C2-symmetrical chiral primary amines were synthesized from chiral BINOL and diamines. Then their catalytic activities in the asymmetric aldol reactions were evaluated, and the result indicated that 1c was the optimal organocatalyst.

Chiral discrimination of α-amino acids has been realized by a C 2-symmetric homoditopic receptor, which is based on a binaphthyl chiral skeleton with 2,2′diisopropoxy substituents and a common binding side arm, (o-carboxamido)-trifluoroacetophe

(Chemical Equation Presented) In this article, we report on the synthesis and conformation of a new family of aromatic oligoamide foldamers based on binaphthol (BINOL) monomers. A series of oligomers with differing chirality of the individual BINOL building blocks and mixed sequences of alternate BINOL and pyridyl building blocks has been synthesized and structurally characterized. NMR and quantum chemical calculations on the basis of ab initio MO theory were performed to obtain insight into the conformational features of these oligomers. It is shown that the combination of these inherently chiral aromatic building blocks provides a novel access to a wide variety of conformationally ordered synthetic oligomers with diverse and dazzling structural architectures distinct from those classically observed.

Chiral 1,5-diaza-cis-decalins have been examined as ligands in the enantioselective oxidative biaryl coupling of substituted 2-naphthol derivatives. Under the optimal conditions employing 2.5-10 mol % of a 1,5-diaza-cis-decalin copper(II) catalyst with oxygen as the oxidant, enantioselective couplings (44-96% ee) could be achieved for a range of 3-substituted 2-naphthols including the ester, ketone, phosphonyl, and sulfonyl derivatives. The relationship between the substitution of the naphthalene starting materials and reactivity/selectivity is determined by several factors which act in concert: (1) the effect of substituents on the oxidation potential of the substrate, (2) the ability of the substrate to participate in a chelated copper complex which depends on (a) the inherent coordinating ability of the 3-substituent and (b) substituent steric interactions that affect chelation between the 2-hydroxyl and 3-substituent, (3) the effect of substituents on dissociation of the product from the copper catalyst.

A variety of 2-naphthols have been selectively oxidized to their corresponding 1,1′-bi-2-naphthols in excellent yields with molecular oxygen using methyltrioxorhenium as catalyst.

Asymmetric oxidative coupling of (S)-1-(3-hydroxy-2-naphthylcarbonyl)pyrrolidine-2-carboxylic acid methyl ester 1 catalyzed by CuCl afforded (S,S,R)-2,2′-dihydroxy-3,3′-bis(2-methoxycarbonyl-1- pyrrolidinylcarbonyl)-1,1′-binapthalene 2 with diastereomeric excess up to 65.9%. (R)-BINOL-3,3′-diacid 3 was obtained in 30% overall yield and 97% e.e. by separating the diastereomers and hydrolyzing 2.

Novel metal salts of binaphthol derivative are provided. The metal salts of the present invention are those represented by the formula of either (1) or (2): The present invention also provides a method for preparing the same from the corresponding binaphthalene derivative.

New BINOL-derived ligands, 3,3′-bis(2-oxazolyl)-1,1′-bi-2-naphthols (BINOL-Box), bearing chiral bis-oxazoline at the 3,3′-carbons, were synthesized from commercially available 1,1′-bi-2-naphthol (BINOL). With the new ligands obtained, we found that asymmetric 1,3-dipolar cycloaddition reaction of N-benzylidenebenzylamine N-oxide (2) to 3-((E)-2-butenoyl)-1,3-oxazolidin-2-one (1) was catalyzed by BINOL-Box-scandium complexes to give isoxazolidine 3 in high yield with high diastereo- and enantioselectivity. For example, the reaction of 1 with 2 catalyzed by a 6 mol% (S,R)-7d and 5 mol% Sc(OTf)3 complex proceeded to give the endo-3 as the major diastereomer with an endo:exo ratio of 97:3 and 87% ee of the endo-product in the presence of 4 ? molecular sieves. Interestingly, the absolute configuration of the major product was changed according to the kind of additive used.

Enantiomeric BINOL has been anchored to aminomethylated polystyrene resin at the 3- and 3,3'-positions of BINOL respectively. The resulting functionalized polymers 4 and 7 have been used as chiral ligands in the Ti- catalytic enantioselective addition of

A new polymer-supported BINOL (1,1′-Bi-2-naphthol) was synthesized by coupling of aminomethyl polystyrene resin and (S)-2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxylic acid. This new ligand was found to be more enantioselective for the asymmetric addition of diethylzinc to aldehydes than its "free" analog [Ti(BINOL)iPrO2]. A range of 57-99% ee's as well as 78-97% yields was obtained, and the electronic properties of the enantioselectivity were also observed.

The newly introduced tittle compounds were found to be efficient chiral auxiliaries for the asymmetric Simmons-Smith cyclopropanation of allylic alcohols and for asymmetric addition of diethylzinc to aldehydes. For example, Simmons- Smith cyclopropanation of cinnamyl alcohol in the presence of N,N,N′,N′-tetraethyl-2,2′-dihydroxy-1, 1′-binaphthyl-3, 3′-dicarboxamide (1b) proceeded with high enantioselectivity of 94% ee and addition of diethylzinc to benzaldehyde in the presence of N,N,N′,N′-tetraisopropyl-2,2′-dihydroxy-1,1′-binaphthyl- 3,3′-dicarboxamide (1e) proceeded with enantioselectivity of 99% ee. Although the reaction mechanism of these reactions is still nuclear, a monomeric seven-membered 2,2′-dihydroxy-1,1′-binaphthyl-3,3′-dicarboxamide (1)-Zn complex is considered to be an active species which catalyzes the above reactions, on the basis of NMR experiments.

Axially chiral synthons for chiral dendrimer construction based on 2,2′-dihydroxy-1, 1′-binaphthalene-3,3′-dicarboxylic acid were prepared, namely, chiral connecting units (3, 6, 8), chiral branching units(10, 12, 14), and chiral surface units (5, 17). Re

N,N,N',N'-Tetraethyl-1,1'-bi-naphthol-3,3'-dicarboxamide (1b) was found to be an effective chiral auxiliary for asymmetric Simmons-Smith cyclopropanation and high enantioselectivity greater than 85percent ee was achieved in the reaction of E-allylic alcohols.

The synthesis of new tetraazacyclophanes is reported.The macrocycles are composed of biaryl units incorporated in the macroring by imination reactions at their 3- and 3'-positions with α,ω-diamines.The biaryl units are substituted at their 2- and 2'-posit