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A modular six-step asymmetric synthesis of two naturally occurring and three non-natural isoflavanones containing tertiary alpha-aryl carbonyls is reported. This synthetic route, utilising a Pd-catalyzed decarboxylative asymmetric protonation, produces isoflavanones in excellent enantioselectivities from 76-97 %. A switch in the sense of stereoinduction was observed when different H+ sources were employed, showing the first example of dual stereocontrol in an asymmetric protonation reaction. The first enantioselective synthesis of the naturally occurring isoflavanones sativanone and 3-o-methylviolanone has been accomplished. Proton haze – Don?t know if I?m comin’ up or down: The first asymmetric synthesis of the naturally occurring isoflavanones, sativanone and 3-O-methylviolanone, containing tertiary alpha-aryl carbonyls, has been accomplished. This was achieved through a Pd-catalyzed decarboxylative asymmetric protonation in excellent enantioselectivities from 76-97 %. A switch in the sense of stereoinduction was observed when different H+ sources were employed.

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

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We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.

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

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Chemistry is traditionally divided into organic and inorganic chemistry. Recommanded Product: (S)-4-(tert-Butyl)-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole. The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent,Which mentioned a new discovery about 148461-16-9

An efficient desymmetrization of -quaternary carbon-containing cyclohexanones using readily available Pd/(S)-tBuPhox and benzylamine as dual catalysts is reported. We describe herein the development of the reaction, exploration of the substrate scope, and studies on the reaction mechanism. The intramolecular coupling reaction leads to the formation of bicyclo[3.3.1]nonanones with a quaternary carbon bridgehead in synthetically useful yields (up to 98%) with high enantioselectivities (up to 98:2 er) and good functional group tolerance (>30 examples). Significantly, aryl and alkenyl bromides as well as less reactive triflates are all compatible substrates for this process. The synthetic versatility of this strategy is demonstrated by scale-up synthesis and diverse transformations of the products into valuable building blocks, including quaternary center-containing dihydronaphthalenes, ring-fused indoles and lactones, tetralones, and 6,6,5-tricycles. Mechanistic studies by computational calculations provide insights into the role of benzylamine in accelerating the reaction rate and enhancing the enantioselectivities.

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

New explortion of (S)-4-(tert-Butyl)-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole

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1,1,2-Trisubstituted alkenes with a single strongly electronic withdrawing activator, which are unreactive electron-deficient alkenes in transition metal-catalyzed [3+2] cycloaddition with vinyl three-membered heterocycles, were used in the Pd-catalyzed asymmetric cycloaddition of vinyl epoxides, affording multifunctionalized tetrahydrofurans in high yields with high diastereo- and enantioselectivities.

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

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A three-component coupling using lithiated indoles, boronate esters and allylic acetates generates chiral indolines with adjacent quaternary stereocenters. Successful stereocontrol required the use of phosphoramidite ligands not previously described for organopalladium chemistry. Mechanistic studies indicate a monodentate PdL intermediate, and a stepwise allylation-aryl/alkyl migration. A protodeborylation strategy was used to install a C-H bond in place of the C-B bond. A photoredox coupling was used to replace C-B bond with a C-C bond in a highly diastereoselective manner. In the specific case of methyl-vinyl ketone, a novel radical-mediated annulation provides polycyclic products with high enantio- and diastereoselectivity.

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

Final Thoughts on Chemistry for (S)-4-(tert-Butyl)-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole

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A highly efficient synthesis of N-allylindoles was realized via palladium-catalyzed asymmetric allylic amination/oxidation sequential reaction of indolines. The N-alkylated indole derivatives were obtained with up to 91% yield and 97% ee.

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

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Copper (II)/RuPHOX-Catalyzed Enantioselective Mannich-Type Reaction of Glycine Schiff Bases with Cyclic Ketimines

A Cu(II)/RuPHOX-catalyzed enantioselective Mannich-type reaction of glycine Schiff bases with cyclic ketimines was developed, affording chiral alpha,ss-diamino acid derivatives in good yields with moderate to good ee and dr values. This provides an efficient methodology for furnishing chiral Cbeta-tetrasubstituted alpha,beta-diamino acid precursors. The catalytic system is compatible with a series of substrates. In addition, an interesting nonlinear effect of the catalyst’s enantiomeric composition on reaction enantioselectivity was observed. (Figure presented.).

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

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A facile and modular synthesis of phosphinooxazoline ligands

The copper(I) iodide catalyzed phosphine/aryl halide coupling procedure of Buchwald et al. provides modular, robust, and scaleable access to phosphinooxazoline (PHOX) ligands. The advantages of this method are highlighted by the convenient synthesis of PHOX liganda with varied steric and electronic properties, which would be challenging to synthesize by other protocols.

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

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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, 148461-16-9, molcular formula is C25H26NOP, introducing its new discovery. Application In Synthesis of (S)-4-(tert-Butyl)-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole

Studies on the enantioselective synthesis of carbazolones as intermediates in aspidosperma and kopsia alkaloid synthesis

Two strategies for the assembly of homochiral carbazolones have been investigated. The first exploited desymmetrisation of 1,3-cyclohexadione derivatives however this failed to deliver satisfactory outcomes. An orthogonal route exploiting palladium catalysed decarboxylative allylation of racemic carbazolone beta-ketoesters has been developed. Herein we report full details on the development of this reaction and clarify apparent discrepancies between our preliminary reports and those of Shao.

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

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Cu(ii)-: TBu-PHOX catalyzed enantioselective malonate addition onto 3-hydroxy 2-oxindoles: Application in the synthesis of dimeric pyrroloindoline alkaloids

An efficient Cu(ii)-PHOX-catalyzed malonate addition onto 3-hydroxy 3-indolyl-2-oxindoles is envisioned to afford excellent enantioselectivities (up to >99% ee) in high chemical yields. Detailed characterization techniques including X-ray, NMR, CV and EPR experiments suggest that a Cu(ii)-complex is involved as an active species in this process. Applying this strategy, an advanced intermediate of cyclotryptamine alkaloids has been synthesized in few steps for a general approach to bis-cyclotryptamine alkaloids.

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