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alpha,alpha-Diphenyl-L-prolinol derivatives with para-bromo substituants in either one or both of the phenyl rings are easily bound to crosslinked polystyrene beads containing phenylboronic acid residues by Suzuki couplings. By using extended reaction periods boronic acid residues that do not take part in the couplings are simply lost by hydrolysis. The polymer-supported (PS) alpha,alpha-diphenyl-L-prolinols were used to catalyse reductions of several prochiral ketones with borane in tetrahydrofuran at 22 C. The expected secondary alcohols were obtained in high chemical yields and ees were generally in the range 79-97 %. One PS catalyst was recycled 14 times without loss of stereochemical performance.

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

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Novel bifunctional chiral squaramide-amine organocatalysts have been developed by rational combination of pyrrolidine and a cinchona alkaloid. The catalysts promoted the enantioselective Michael addition of both mono-and diketones to a broad range of nitroalkenes providing the corresponding products in moderate to high yields with excellent enantioselectivities and diastereoselectivities (up to 96% yield, 96% ee, 98:2 dr) under mild conditions. These results demonstrate that the assembly of two chiral privileged skeletons, pyrrolidine and cinchonine with a squaramide linker is a useful strategy to reach a wider substrate scope, high reaction efficiency and enantioselectivity. The match of the chiralities between two backbones embedded in the catalysts is also critical for improving enantioselectivity. ARKAT-USA, Inc.

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

Discovery of (S)-Diphenyl(pyrrolidin-2-yl)methanol

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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, 112068-01-6, molcular formula is C17H19NO, introducing its new discovery. Application In Synthesis of (S)-Diphenyl(pyrrolidin-2-yl)methanol

Breaking kamp: A catalytic route toward chiral alpha-alkyl-beta- ketoesters using the title reaction of alpha-alkyl diazoester with aldehydes has been developed (see scheme). The reaction proceeds with high to excellent enantioselectivities and this methodology was applied to a concise two-step synthesis of the natural pheromone sitophilate. Copyright

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

Some scientific research about (S)-Diphenyl(pyrrolidin-2-yl)methanol

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New chiral compounds, (S)-N-acylpyrrolidinylmethanols (1b-f and 1h), were synthesized and chiral methyltitanium diisopropoxides (2a-h) were prepared from 1a-h.Enantioselective carbon-carbon bond formation between aromatic carbaldehydes and 2a-h was achieved in yields of 90-97 percent and 10.5-54.1 percent ee.The chiral auxiliaries (1a-h) were recovered in almost quantitative yields without any loss of optical purity.Keywords: (S)-N-acylpyrrolidinylmethanol; carbon-carbon bond formation; enantioselective reaction; methyltitanium diisopropoxide; (R)-1-(1-naphthyl)ethanol; (R)-1-phenylethanol; (S)-prolinol

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

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Effect of ligand structure on the zinc-catalyzed Henry reaction. Asymmetric syntheses of (-)-denopamine and (-)-arbutamine

(Matrix presented) Syntheses of variously modified ligands for the dinuclear zinc catalysts for the asymmetric aldol and nitroaldol (Henry) reactions are reported. Catalytic enantioselective nitroaldol reactions promoted by these modified ligands led to efficient syntheses of the beta-preceptor agonists (-)-denopamine and (-)-arbutamine.

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

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In search of diamine analogs of the alpha,alpha-diphenyl prolinol privileged chiral organocatalyst. Synthesis of diamine derivatives of alpha,alpha-diphenyl-(S)-prolinol and their application as organocatalysts in the asymmetric Michael and Mannich reactions

This paper describes improved reaction conditions for the substitution of the hydroxyl group in (S)-diphenyl(pyrrolidin-2-yl)methanol by the azide group, which was then reduced to the diamine derivative. We examined two protecting groups (N-Bn and N-Boc) on the pyrrolidine nitrogen in order to functionalize the primary amino group into various amide, alkylated amine, sulfonamide, thiourea and triazole derivatives. Notably, carefully controlled conditions were required to generate the desired derivatives from the sterically hindered benzhydrylamine moiety. Unexpectedly, upon removal of the N-protecting group in derivatives containing electrophilic polar double bonds (C=S, C=O) cyclization took place, affording products such as amidines. The target compounds were evaluated as bifunctional organocatalysts in the asymmetric Michael and Mannich addition reactions. (S)-2-(Azidodiphenylmethyl)pyrrolidine (S)-7 was identified as the most efficient organocatalyst among the various diamine derivatives of alpha,alpha-diphenyl-(S)-prolinol prepared in this work.

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

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Lewis acid-promoted nitroolefination of enol silyl ethers via an addition elimination process

Lewis acid-promoted nitroolefination of enol silyl ethers has been developed. Enol ethers 1, 4, 5, and 6 derived from lactones and lactams furnished nitroolefines 2, 7, 8, and 9, respectively in 60 – 99% yields by the treatment with 3 in the presence of Lewis acids. Asymmetric nitroolefination of 5a and 6a with 12 gave 8a and 9a in 75% and 73% ee, respectively.

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

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Mukaiyama-Michael reactions with acrolein and methacrolein: A catalytic enantioselective synthesis of the C17-C28 fragment of pectenotoxins

Enantioselective iminium-catalyzed reactions with acrolein and methacrolein are rare. A catalytic enantioselective Mukaiyama-Michael reaction that readily accepts acrolein or methacrolein as substrates, affording the products in good yields and 91-97% ee, is presented. As an application of the methodology, an enantioselective route to the key C17-C28 segment of the pectenotoxin using the Mukaiyama-Michael reaction as the key step is described.

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

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Design, synthesis and structure of new chiral squaric acid monoaminoalcohols and diaminoalcohols and their use as catalysts in asymmetric reduction of ketones and diketones

Many chiral squaric acid aminoalcohols and C2-symmetric diaminoalcohols have been synthesized and their in situ formed chiral boron heterocycles have been used as catalysts for the enantioselective reduction of prochiral ketones and diketones by borane to give alcohols with up to 99% enantiomeric excess and 99% yield. The effects of solvent, catalyst-substrate ratio and temperature were also investigated.

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

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Highly Enantioselective Epoxidation of alpha,beta-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me3Si)2N]3RE(mu-Cl)Li(THF)3 with Phenoxy-Functionalized Chiral Prolinols

A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)2N]3RE(mu-Cl)Li(THF)3 (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee. (Figure Presented).

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