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New bidentate phosphites were prepared starting from BINOL and H8-BINOL. Utilization of these ligands in the copper-catalyzed enantioselective conjugate addition of trimethylaluminum to 2-cyclohexenone afforded 3-methylcyclohexanone with up to 96% e.e. The scope of this process using various copper sources was investigated.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A new series of monodentate phosphites based on the rigid, axially chiral monoesterified H8-BINOL, which are easy to prepare from the readily accessible phosphorylating reagents (Sa)- or (Ra)-1,1?-binaphthyl-2,2?-diylchlorophosphite and (Sa)- or (Ra)-1,1?-H8-binaphthyl-2,2?-diylchlorophosphite, have been synthesized. All ligands were purified on a silica gel column under a nitrogen atmosphere with moderate yields, and were white solids and air-stable at room temperature. These ligands afforded good to excellent enantioselectivities in the Cu-catalyzed 1,4-conjugate addition of 2-cyclohexenone with nucleophiles Et2Zn (96% ee) and with Ph2Zn (65% ee), 2-cyclopentenone with Et2Zn (95% ee), 2-cycloheptenone with Et2Zn (76% ee), and 5,6-dihydro-2H-pyran-2-one with Et2Zn (90% ee). In the Rh-catalyzed asymmetric hydroformylation of styrene, these ligands showed a chemoselectivity of >99% in aldehydes, and a satisfactory branched over linear ratio (96/4). Moreover, the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the BINOL-based or H8-BINOL-based phosphocycle.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The triple enantioselective enzyme-catalyzed transacylation of rac-1-indanol with rac-1-,1?-bi-2-naphthyl-2,2?-dibutyrate afforded(S)-1 -indanol, (R)-1 -indanylbutyrate, (S)-1,1?-bi-2-naphthyl-2,2?-diol, and (R)-1,1?-bi-2-naphthyl-2,2?-dibutyrate.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Archives for Chemistry Experiments of (R)-[1,1′-Binaphthalene]-2,2′-diol

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In the presence of a catalytic amount of ammonium chiral borate salt, asymmetric Friedel-Crafts alkylation of indoles with alpha,beta-disubstituted enals proceeded to give the corresponding 1,4-addition products with moderate enantioselectivities.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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We recently noticed that a number of the ChemDraw structures in our original paper were drawn incorrectly as their meta fluoro to boron isomers, rather than their correct para fluoro to boron isomers. The graphical abstract and scheme on page 427 were affected. The corrected version is given below. (Figure Presented).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A binaphthol-based phosphoramidite ligand (4.2 mol%) having a C2-symmetric chiral amine moiety was examined for enantioselective 1,4-additions of dialkylzinc reagents to various macrocyclic, cyclic, and acyclic enones catalyzed by copper triflate·toluene complex (2 mol%) to afford high enantiomeric excess (up to >95% ee).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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By complexation with optically active 2,2′-dihydroxy-1,1′-binaphthyl, alkyl aryl and dialkyl sulfoxides were resolved very efficiently.Reversely, by complexation with optically active alkyl aryl or dialkyl sulfoxides, 2,2′-dihydroxy-1,1′-binaphthyl was resolved very efficiently.In all cases, 100percent optically pure (+)- and (-)-enantiomers were obtained in good yields.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a?g bearing binaphthyl units have been synthesized by the Et2AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a?g with 1,1?-binaphthalene-2,2?-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)-3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher glum values in the solid state, probably due to intermolecular interactions. Because (R,R)-3 h recorded relatively low glum values, the diastereomer (R,S)-3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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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.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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An intramolecular SNAr reaction makes the synthesis of enantiopure MAP(O)-type P,N ligands in high yields possible (see scheme) and demonstrates that the synthetic potential of the 85-year-old Staudinger reaction between phosphanes and azides is still far from being exhausted. Nf = nonafluorobutanesulfonate.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI