A new application about (R)-[1,1′-Binaphthalene]-2,2′-diol

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The development and application of a novel linked-1,1?-binaphthol (linked-BINOL) as an approach towards practical asymmetric multifunctional catalysis is described. Linked-BINOL was first designed to increase the stability of a Ga-Li-BINOL complex against ligand exchange with 4-methoxyphenol. An oxygen-containing linked-BINOL, which is a semi crown ether, was effective in both promoting the formation of a monomer complex and increasing the stability of the Ga-Li complex. A Ga-Li-linked-BINOL complex promoted the epoxide opening reaction in up to 96% enantiomeric excess (ee). Second, based on the X-ray structural information of the Ga-Li-linked-BINOL complex, we designed a more stable lanthanide linked-BINOL complex. An air-stable, storable, and reusable La-linked-BINOL complex promoted the Michael reaction in up to >99% ee. The catalyst activity remained unchanged after storage under air for 4 weeks. Calculations suggested that the linked-BINOL would function as a pentadentate ligand in a lanthanum complex, thus efficiently improving the stability of the complex. Finally, the linked-BINOL was applied to a new homobimetallic multifunctional catalysis. A dinuclear Zn-Zn-linked-BINOL complex promoted the enantio- and diastereoselective direct aldol reaction in up to 99% ee, where one Zn cation might function as a Lewis acid and the other Zn-phenoxide as a Bronsted base.

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The fundamental properties of a series of organic monosilanols, silanediols, disiloxanediols, and known hydrogen-bonding organocatalysts have been examined in the gas phase using computational and experimental mass spectrometry methods. The organosilicon diol molecules contain dual hydrogen-bonding groups that were designed as potential hosts and hydrogen-bonding catalysts. Newly measured acidities are reported, and implications regarding solvent effects, catalysis, and molecular recognition are discussed.

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Several syn and anti atropisomers of 2-(5-benzo[b]fluorenyl)-2?-hydroxy-1,1?-binaphthyl and related compounds were synthesized from 1,1?-binaphthyl-2,2?-diol (BINOL). It was possible to separate the syn and anti atropisomers by silica gel column chromatography. The syn atropisomers are potential hetero-bidentate ligands for complex formation with metals. By starting from enantiomerically pure (R)-(+)-BINOL and (S)-(-)-BINOL, four optically active syn atropisomers and two anti atropisomers with high enantiomeric purity were obtained. The structures of two syn atropisomers and one anti atropisomer were established by X-ray structure analyses.

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A pair of novel chiral one-dimensional compounds with the general formula [Cd(NO3)2L2]·THF (where L is R- or S-2,2?-bis(methoxymethoxy)-6,6?-bis(4-pyridyl)-1,1?-binaphthyl) for the first time show circularly polarized luminescence, two-photon excited fluorescence, and second harmonic generation activity.

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Optically active overcrowded alkenes were synthesized by employing bis- beta-naphthol as a chiral template during an intramolecular coupling reaction. The major isomer 2 has a unique helical structure with twisted and folded structural moieties. Removal of the chiral template afforded overcrowded thioxanthylidene 3 with 96% ee, which indicates that no racemization or isomerization of the enantiomers took place.

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The condensation of the resolved C2-symmetric benzaldehyde, 1,2,3,4,5,6,7,8-octahydro-1:4,5: 8-dimethanoanthracene-9-carboxyaldehyde, with pyrrole produced the first chiral tetraarylporphyrin 1 exhibiting D4-symmetry. The resolved benzaldehyde was synthesized in seven steps from p-benzoquinone and cyclopentadiene and included a resolution via diastereomeric ketals. A manganese chloride complex of porphyrin 1 was used as a catalyst for the asymmetric epoxidation of aromatic substituted alkenes in the presence of excess sodium hypochlorite in up to 7,200 turnovers and up to 76% e.e and >90% yield.

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Chiral cyclic compounds exhibited light-driven twisting by means of trans-cis photoisomerization in 1,4-dioxane solution, a neat film, and a liquid-crystalline host. The Royal Society of Chemistry.

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The first optically active rigid covalently linked by enantiomerically pure (R)- or (S)-BINOL metal-free phthalocyanine dimers have been prepared and characterized using electronic absorption, CD, MCD, MS, and NMR techniques as well as semi-empirical molecular orbital calculations.

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Metal catalyst and ligand design,
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The axially chiral monophosphine 2-(diphenylphosphino)-2′-methoxy-1,1′- binaphthyl (MeO-MOP) is a versatile ligand. We report a shorter (four steps from chiral BINOL), more atom-economical synthetic route to MeO-MOP. (R)-BINOL is transformed into its monomethyl ether by the Mitsunobu reaction, and the latter is reacted with triflic anhydride to give its triflate. The C-P coupling of the triflate and diphenylphosphine oxide catalyzed by palladium give a phosphine oxide, the precursor of (R)-MeO-MOP, which is reduced with trichlorosilane to furnish (R)-MeO-MOP.

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Metal catalyst and ligand design,
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Mechanistic studies on Cu-catalyzed asymmetric additions of alkylzirconocene nucleophiles to racemic allylic halide electrophiles were conducted using a combination of isotopic labeling, NMR spectroscopy, kinetic modeling, structure-activity relationships, and new reaction development. Kinetic and dynamic NMR spectroscopic studies provided insight into the oligomeric Cu-ligand complexes, which evolve during the course of the reaction to become faster and more highly enantioselective. The Cu-counterions play a role in both selecting different pathways and in racemizing the starting material via formation of an allyl iodide intermediate. We quantify the rate of Cu-catalyzed allyl iodide isomerization and identify a series of conditions under which the formation and racemization of the allyl iodide occurs. We developed reaction conditions where racemic allylic phosphates are suitable substrates using new phosphoramidite ligand D. D also allows highly enantioselective addition to racemic seven-membered-ring allyl chlorides for the first time.1H and2H NMR spectroscopy experiments on reactions using allylic phosphates showed the importance of allyl chloride intermediates, which form either by the action of TMSCl or from an adventitious chloride source. Overall these studies support a mechanism where complex oligomeric catalysts both racemize the starting material and select one enantiomer for a highly enantioselective reaction. It is anticipated that this work will enable extension of copper-catalyzed asymmetric reactions and provide understanding on how to develop dynamic kinetic asymmetric transformations more broadly.

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Metal catalyst and ligand design,
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