Awesome Chemistry Experiments For (S)-[1,1′-Binaphthalene]-2,2′-diol

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Highly Enantioselective 1,4-Addition of Diorganozinc Reagents to Cyclic Enones Using Chiral Diphosphite Ligands Derived from H8-Binaphthol

(Matrix Presented) High enantioselectivities have been achieved in the 1,4-addition of dialkylzincs to 2-cyclopentenone, 2-cyclohexenone, and 2-cycloheptenone with ee values up to 99% by using chiral aryl diphosphite ligands derived from H8-binaphthol.

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Metal catalyst and ligand design,
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An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles

Combining micellar electrokinetic capillary chromatography (MEKC) and nuclear magnetic resonance (NMR) experimentation, we shed light on the structural basis for the chirally selective solubilization of atropisomeric binaphthyl compounds by bile salt micelles comprised of cholate (NaC) or deoxycholate (NaDC). The model binaphthyl analyte R,S-BNDHP exhibits chirally selective interactions with primary micellar aggregates of cholate and deoxycholate, as does the closely related analyte binaphthol (R,S-BN). Chiral selectivity was localized, by NMR chemical shift analysis, to the proton at the C12 position of these bile acids. Correspondingly, MEKC results show that the 12alpha-OH group of either NaC or NaDC is necessary for chirally selective resolution of these model binaphthyl analytes by bile micelles, and the S isomer is more highly retained by the micelles. With NMR, the chemical shift of 12beta-H was perturbed more strongly in the presence of S-BNDHP than R-BNDHP. Intermolecular NOEs demonstrate that R,S-BNDHP and R,S-BN interact with a similar hydrophobic planar pocket lined with the methyl groups of the bile salts, and are best explained by the existence of an antiparallel dimeric unit of bile salts. Finally, chemical shift data and intermolecular NOEs support different interactions of the enantiomers with the edges of dimeric bile units, indicating that R,S-BNDHP enantiomers sample the same binding site preferentially from opposite edges of the dimeric bile unit. Chirality 28:525?533, 2016.

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Acetyl-BINOL as mimic for chiral beta-diketonates: A building block for new modular ligands

alpha-Acetyl-(S)-BINOL was prepared by ortho-lithiation and subsequent acetylation of acetal-protected (S)-BINOL. The beta-hydroxyketone moiety of this compound is herein a structural mimic for a beta-diketonate and forms six-membered chelates with transition metal ions. The second hydroxy-function was submitted to esterification with several carboxylic acids bearing another donor function, thus, new tridentate chiral ligands were obtained. Out of this library the l-proline-alpha-acetyl-(S)-BINOL-ester was identified to be most effective for the titanium-mediated addition of Et2Zn to PhCHO yielding the respective secondary alcohol with up to 93% ee, which is better than with using (S)-BINOL itself. Besides a solvent dependency (use of MeCN is optimal), the proper choice of the counter-ion is crucial: anion exchange of bromide by trifluoroacetate gave a significant increase of enantioselectivity. Copyright

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, Application In Synthesis of (S)-[1,1′-Binaphthalene]-2,2′-diol, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 18531-99-2, Name is (S)-[1,1′-Binaphthalene]-2,2′-diol, molecular formula is C20H14O2. In a Article, authors is Schanz, Hans-Joerg£¬once mentioned of 18531-99-2

Improved resolution methods for (R,R)- and (S,S)-cyclohexane-1,2-diamine and (R)- and (S)-BINOL

Starting from inexpensive L-(+)-tartaric acid, it was possible to resolve and obtain pure both enantiomers of trans-cyclohexane-1,2-diamine 1 and thence both enantiomers of BINOL 2, two of the most powerful, chiral inducing backbones in asymmetric catalysis. The modified method is very economic, not only due to an almost doubling of the overall yields of enantiomerically pure compounds (86% 1, 83% 2) but also due to the easy recovery of resolving agent 1 [66% (R,R)-1, 79% (S,S)-1] in the BINOL resolution. An improvement in the yield of the preparation of racemic BINOL is also recorded.

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Synthesis of novel chiral bidentatephosphite ligands derived from the pyranoside backbone of monosaccharides and their application in the Cu-catalyzed conjugate addition of dialkylzinc to enones

A series of novel bidentatephosphite ligands, derived from methyl 3,6-anhydro-alpha-d-glucopyranoside and chlorophosphoric acid diaryl ester, were easily synthesized. These ligands were successfully employed in the Cu-catalyzed asymmetric conjugate 1,4-addition of the organozinc reagents diethylzinc and/or dimethylzinc to enones. The stereochemically matched combination of glucopyranoside and (R)-H8-binaphthyl in ligand 2,4-bis{[(R)-1,1?-H8-binaphthyl-2,2?-diyl] phosphite}-methyl 3,6-anhydro-alpha-d-glucopyranoside was essential to afford 85% ee for 3-ethylcyclohexanone with an (S)-configuration in THF, using Cu(OTf)2 as a catalytic precursor. When the reaction was carried out at lower temperatures, changing from -10 to -80 C, a marginal influence of the temperature on the enantioselectivity of the reaction was observed. The presence of the methyl substituent at the 1-position of the glucopyranoside skeleton had a negative effect on the enantioselectivity in the 1,4-addition of ZnEt2 to acyclic enones.

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Synthesis and Reactivity of Chiral, Wide-Bite-Angle, Hybrid Diphosphorus Ligands

Effective and modular synthetic approaches toward phosphine-phosphite ligands and phosphine-phosphonite ligands featuring a diphenyl ether backbone have been developed. The phosphine-phosphite ligands are obtained by a two-step protocol from 2-bromo-2?-methoxydiphenyl ether. The phosphine-phosphonite ligands are prepared in a four-step synthetic protocol that involves a novel, unsymmetrical diphenyl ether derived phosphine-phosphorusdiamide as key building block. Structural studies on PtII complexes with either phosphine-phosphite or phosphine-phosphonite ligands indicate strict cis coordination for these ligand systems. High-pressure NMR spectroscopy studies of Rh complexes under syngas indicate the presence of two ea isomers for Rh(H)(CO)2(PP). The existence of this mixture is further supported by high-pressure IR spectroscopy studies. In order to benchmark the activity and selectivity of these novel, wide-bite-angle, mixed-donor ligands, they were screened in Pd-catalyzed asymmetric allylic alkylation as well as Rh-catalyzed hydrogenation and hydroformylation reactions. The ligands give 100-% conversion and low-to-moderate enantioselectivity in the allylic alkylation of 1,3-diphenyl-2-propenyl acetate and cyclohexyl-2-enyl acetate with dimethyl malonate. In the hydroformylation of styrene, good conversion and regioselectivities are achieved but only moderate enantioselectivity. The ligands give good conversions in asymmetric hydrogenation of typical substrates, with good-to-excellent enantioselectivities of up to 97-% depending on the substrate. Copyright

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BINOL derivatives with aggression-induced emission

As fluorescent probes, the small Stokes shift and ACQ effect limit the application of BINOL derivatives. Herein, a new series of BINOL derivatives were synthesized which could be turned from ACQ to AIE fluorophores by changing the electron withdrawing group. Among these compounds, BIN-COP exhibits an obvious AIE property with low cytotoxicity. The bioimaging performance indicated that the designed fluorophores could be successfully used for bioimaging.

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THREE COMPONENT CO-CRYSTAL FORMATION BETWEEN DIASTEREOMERIC MIXTURES OF 3-ALKYL-4-((S)-1’PHENYLETHYLAMINO) BUTANOIC ACID AND OPTICALLY PURE 1, 1′-BI-2-NAPHTHOL

A ternary co-crystal consisting of 1 :0.5:0.5 molar proportion of (S)-1,1′-bi-2-naphthol, 3(S)-propyl-4-[(S)1 ‘-phenyl-ethylamino]-butanoic acid and 3(R)-propyl-4-[(S)1′- phenyl-ethylamino]-butanoic acid having characteristic powder X-ray diffraction pattern with 2Theta values of 8.41, 9.38, 10.32, 12.16, 15.52, 15.51, 17.84, 17.95, 19.16, 20.37, 21.74, 22.55, 24.44, 25.65, 28.40, 29.15, 29.69, 31.31, 33.54, 34.40, 35.43 (¡À0.2) and having differential scanning calorimetric peak at about 189.23 C when analyzed at the rate of heating of 10C per minute and process for preparing the same. A process for resolution of (S)-1,1′-bi-2-naphthol from RS-1,1’-bi-2-naphthol.

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Effects of solvent on inclusion complexation of a chiral dipeptide toward racemic BINOL

The effects of reaction solvent on inclusion complexation of a chiral dipeptide (3S,6S)-1 derived from (S)-proline toward racemic BINOL was investigated, discovering that the reaction solvent played a crucial role in determining the inclusion complexation behavior of dipeptide (3S,6S)-1 toward rac-BINOL. (3S,6S)-1 did not show any chiroselective or achiroselective complexation toward rac-BINOL in polar protic solvents such as methanol and ethanol, polar aprotic solvents including trichloromethane and THF, while in polar aprotic solvent ethyl acetate and apolar aprotic solvents benzene, (3S,6S)-1 displayed achiroselective complexation toward rac-BINOL. However, the resulting heterocomplex HC-2 from benzene and HC-3 from ethyl acetate have a different composition. Single crystal X-ray diffraction analysis demonstrates that the two heterocomplexes are formed via different H-bond interaction patterns, in which the reaction solvent has a dramatic effect. Furthermore, this work provides a relatively green method for quantitative enantiomeric enrichment of nonracemic BINOL, in which unacceptable and toxic benzene was replaced by ethyl acetate.

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 18531-99-2, molcular formula is C20H14O2, introducing its new discovery. Recommanded Product: (S)-[1,1′-Binaphthalene]-2,2′-diol

Polymer-carrying optically active binaphthyl type oxazoline compound

A polymer-carrying optically active binaphthyl type oxazoline compound having axial asymmetry, represented by the following general formula (1) 1(wherein R1 and R2 may be the same or different from each other and each represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms or the like; R3 is a hydrogen atom or ?R5?X?R6; R4 is a hydrogen atom or the like; R5 is a straight- or branched-chain aliphatic hydrocarbon chain which may have a directly or indirectly bonded substituent; X is CH2, CO2, O, CONR7 or NR7; R6 is a directly or indirectly bonded polymer; and R7 is a hydrogen atom or the like), and to a transition metal complex which uses the compound as the ligand.

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