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Bridging 2,3 and 2?,3? positions in 2,2?-dihydroxy-1, 1?-binaphthyl and 2,2?-diamino-1,1?-binaphthyl, respectively, resulted in formation of chiral O- and N-bis-tricyclic compounds accessible in 4 steps from known 3,3?-diiodo precursors. In both cases, 2-fold ring closing metathesis of tetraallyl intermediates proceeded regioselectively to give tetrahydrobinaphtho[2,3-b]oxepine and -azepine, respectively. In case of the N-mesyl-N-allyl precursor, three, at room temperature separable, rotamers were isolated and characterized by NMR spectroscopy and X-ray structure determination. Their interconversion (process I) was followed by NMR, yielding rate constants and thermodynamic parameters. The rotamers with either C 1 or C2 symmetry were stereospecifically cyclized to conformatively moderately stable bis-sulfonamides. Also in this case, the kinetics of their interconversion (process II) was investigated and from two of them the crystal structure was determined. Processes I and II were investigated by a DFT method, M06-2X, to gain insight into electronic and steric peculiarities responsible for the remarkable conformative stabilities. Transition state geometries and energies were calculated and compared with empirical data.

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

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Practical and efficient protocols to obtain highly hindered polyanionic chelating ligands based on bis-(3,5-di-tert-butyl-2-hydroxybenzamido) compounds are reported here. N-3,5-di-tert-Butylsalicyloyloxysuccinimide was treated with aliphatic diamines to form aliphatic hydrocarbon-linked bis-amides 4a-4g. Aromatic diamines required more powerful electrophile, thus the corresponding benzylated acid chloride was used to form aromatic hydrocarbon-linked bis-amides 8a-8d. The yields ranged from good to very good and showed that choosing the right acylating agent is a key point in this synthesis. All the compounds were characterized by elemental analysis, IR, MS and NMR.

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

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Cation-binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10?20 mol % KOt-Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo-selectivity was observed, generating 1,2-addition products exclusively over 1,4-addition products. UV-vis analysis revealed the pendant oligo-ether group of the catalyst strongly binds to the potassium cation (K+) with 1:1 binding stoichiometry (Ka=6.6×105 m?1).

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

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Traditional methods are ill-suited for the synthesis of ortho,ortho-biphenols, a structural motif found in many polyphenolic natural products, as well as synthetically useful compounds such as the chiral ligands binol, vapol, and vanol. The new route consists of a radical-based reaction of an acetal-tethered biphenyl ether substrate and subsequent hydrolytic cleavage of the dibenzo-1,3-dioxepine intermediate. Copyright

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

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A series of chiral Ag(I) and Cu(II) complexes have been prepared from the reaction between AgX (X = NO3, PF6, OTf) or CuX 2 (X = Cl, ClO4) and chiral biaryl-based N-ligands. The rigidity of the ligand plays an important role in the Ag(I) complex formation. For example, treatment of chiral N3-ligands 1-3 with half equiv of AgX (X = NO3, PF6, OTf) gives the chiral bis-ligated four-coordinated Ag(I) complexes, while ligand 4 affords the two-coordinated Ag(I) complexes. Reaction of AgX with 1 equiv of chiral N4-ligands 5, 7, 8 and 10 gives the chiral, binuclear double helicate Ag(I) complexes, while chiral mono-nuclear single helicate Ag(I) complexes are obtained with N 4-ligands 6 and 9. Treatment of either N3-ligand 1 or N4-ligand 9 or 10 with 1 equiv of CuX2 (X = Cl, ClO 4) gives the mono-ligated Cu(II) complexes. All the complexes have been characterized by various spectroscopic techniques, and elemental analyses. Seventeen of them have further been confirmed by X-ray diffraction analyses. The Cu(II) complexes do not show catalytic activity for allylation reaction, in contrast to Ag(I) complexes, but they do exhibit catalytic activity for Henry reaction (nitroaldol reaction) that Ag(I) complexes do not.

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

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Asymmetric transfer hydrogenation of ketimines with trichlorosilane: Structural studies

We report structural and mechanistic studies on the organocatalytic asymmetric transfer hydrogenation of ketimines with trichlorosilane. Amines were obtained in good yields and moderate enantioselectivities. Both experiment and computation were utilized to provide an improved understanding of the mechanism. Georg Thieme Verlag Stuttgart.

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

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Asymmetric 1,3-dipolar cycloaddition reactions of nitrile oxides catalyzed by chiral binaphthyldiimine-Ni(II) complexes

Asymmetric cycloaddition reactions between several nitrile oxides and 3-(2-alkenoyl)-2-oxazolidinones and 2-(2-alkenoyl)-3-pyrazolidinone derivatives were carried out in the presence of chiral binaphthyldiimine (BINIM)-Ni(II) complexes as catalysts. Using (tf)-BENM-4(3,5-xylyl)-2QN-Ni(II) complex (30 mol %), good regioselectivity (4-Me/5-Me = 85:15) along with high enantioselectivity (96% ee) of the 4-Me adduct were obtained for the reaction between isolable 2,4,6-trimethylbenzonitrile oxide and 3-crotonoyl-5,5-dimethyl-2-oxazolidinone. Substituted and unsubstituted benzonitrile oxides and aliphatic nitrile oxides, which were generated from the corresponding hydroximoyl chloride in the presence of MS 4A, were reacted with 3-crotonoyl-5,5-dimethyl-2-oxazolidinone, 5,5-dimethyl-3-(2-pentenoyl)-2-oxazolidinone, 5,5-dimethy-3-[3-(ethoxycarbonyl) propenoyl]-2-oxazolidinone, 1-benzyl-2-crotonoyl-5,5-dimethyl-3-pyrazolidinone, and 1-ben-zyl-2-[3-(ethoxycarbonyl)propenoyl]-5,5-dimethy-3-pyrazolidinone in the presence of (K)-BENM-4Ph-2QN-Ni(II) or (tf)-BENM-4(3,5-xylyl)-2QN-Ni(II) complexes (10-30 mol %) as catalysts to give the corresponding cycloadducts in high yields, with high regioselectively (4-R/5-R = 85:15-99:1) and with moderate to high enantioselectivities (42-95% ee) of the 4-R adducts. Higher enantioselectivities and regioselectivities were obtained for the reactions using pyrazolidinone derivatives as the dipolarophiles. For the cycloadditions of 2-(2-alkenoyl)-1-benzyl-5,5-dimethyl-3-pyrazolidinones catalyzed by (tf)-BENM-4(3,5-xylyl)-2QN-Ni(II) complex (30 mol %), the enantioselectivity varied from 75% to 95% ee. The reactions between several nitrile oxides and 2-acryloyl-1-benzyl-5,5-dimethyl-3-pyrazolidinone in the presence of (R)-BINIM-4(3,5-xylyl)-2QN-Ni(II) complex (10 mol %) resulted in enantioselectivities (79-91% ee) that exceed those of previously reported enantioselective cycloadditions of acrylic acid derivatives. Furthermore, studies using a molecular modeling program using PM3 calculations were carried out to gain insight into the mechanisms of the asymmetric induction. 2009 American Chemical Society.

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

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Asymmetric cyclopropanation and aziridination reactions of olefins catalyzed by Cu(I)-binaphthyldiimine complexes

The chiral Cu(I)-N,N?-bis(2,6-dichlorobenzylidene)-1,1?-binaphthyl-2, 2?-diamine complex was found to be an efficient catalyst for asymmetric cyclopropanation and aziridination reactions of olefins with l-menthyl diazoacetate and [N-(p-tolylsulfonyl)imino]phenyliodinane, respectively. Among mono- and disubstituted olefins, 1,1-diarylethylenes showed extremely high enantioselectivities (up to 98% ee) in the cyclopropanation reactions in the presence of a chiral Cu(I)-catalyst (2 mol%). In the case of aziridination reactions catalyzed by the same Cu(I)-catalyst (10 mol%), the reaction of trans-substituted 3-aryl-2-propenoates and 1-substituted trans-3-aryl-2-propen-1-ones showed satisfactory results in term of the enantioselectivities (up to 98% ee).

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

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Azoarenes with opposite chiral configurations: Light-driven reversible handedness inversion in self-organized helical superstructures

On the other hand: Azoarene compounds with axially chiral binaphthyl units of the same and opposite chiral configurations were doped into achiral liquid crystals (LCs). They were found to efficiently induce self-organized helical superstructures, which could be reversibly tuned by light irradiation using trans-cis photoisomerization to change the handedness of the helix (see scheme) in LC hosts. Copyright

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

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L-proline diamides with an axially chiral binaphthylene backbone as efficient organocatalysts for direct asymmetric aldol reactions: The effect of acetic acid

A series of L-proline diamides derived from optically active 1,1?-binaphthyl-2,2?-diamines have been synthesized in good yields and their catalytic abilities as organocatalysts in direct asymmetric aldol reactions have been evaluated. Among these organo-catalysts, bis(prolinamides) exhibit higher catalytic abilities. The aldol reaction of arylaldehydes with acetone or cyclohexanone proceeds smoothly using the organocatalyst (10 mol%) in the presence of acetic acid (10 mol%) as an additive in toluene at -40C for 48-72 hours to give the corresponding aldol products in high yields (<90%) and with good to high enantioselectivities (<98%) and high anti-diastereoselectivities (<98:2). Georg Thieme Verlag Stuttgart. I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 18741-85-0, help many people in the next few years.Recommanded Product: (R)-[1,1′-Binaphthalene]-2,2′-diamine

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