404868-29-7

Upstream product

• 73930-97-9 3-acetoxy-1,3-diphenylpropene 
• 108-59-8 malonic acid dimethyl ester 
• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 105-53-3 diethyl malonate 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 

Relevant academic research and scientific papers

Twofold C?H Activation-Based Enantio- and Diastereoselective C?H Arylation Using Diarylacetylenes as Rare Arylating Reagents

C?H bond activation has been established as an attractive strategy to access axially chiral biaryls, and the most straightforward method is direct C?H arylation of arenes. However, the arylating source has been limited to several classes of reactive and bulky reagents. Reported herein is rhodium-catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes for enantio- and diastereoselective construction of biaryls with both central and axial chirality. This twofold C?H activation reaction stays contrast to the previously explored Miura–Satoh type 1:2 coupling of arenes and alkynes in terms of chemoselectivity and proceeded under mild conditions with the alkyne acting as a rare arylating reagent. Both C?H activation events are stereo-determining and are under catalyst control, with the 2nd C?H activation being diastereo-determining in a remote fashion. Analysis of the stereochemistry of the major and side products suggests moderate enantioselectivity of the initial C?H activation–desymmetrization process. However, the minor (R) rhodium vinyl intermediate is consumed more readily in undesired protonolysis, eventually resulting in high enantio- and diastereoselectivity of the major product.

Palladium-catalyzed atroposelective coupling-cyclization of 2-isocyanobenzamides to construct axially chiral 2-aryl- And 2,3-diarylquinazolinones

A palladium-catalyzed imidoylative cycloamidation of N-alkyl-2-isocyanobenzamides with 2,6-disubstituted aryl iodides, affording unprecedented axially chiral 2-arylquinazolinones, has been developed with good yields and atroposelectivities. In this coupling-cyclization process, the biaryl linkage and the heteroaromatic ring are formed sequentially in one step. When N-(2,4dimethoxyphenyl)-2-isocyanobenzamide is applied as a substrate, 2,3-diarylquinazolinones containing two stereogenic axes are produced with moderate diastereoselectivity and good enantioselectivities.

d-Fructose Based Spiro-Fused PHOX Ligands: Palladium Complexes and Application in Catalysis

Phosphinooxazoline (PHOX) ligands are an important class of ligands in asymmetric catalysis. Recently we reported on the synthesis of d-fructose based spiro-fused PHOX ligands. Here, we now present the application of these ligands in asymmetric alkylation

New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-allosamine in Pd-catalysed asymmetric allylic alkylation

New phosphine-imine and phosphine-amine chiral ligands which were easily prepared from D-gluco-, D-galacto- and D-allosamine furnished a high level of enantiomeric excess (up to 99%) in the Pd(0)-catalysed asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate with malonates.

Amino-P Ligands from Iminosugars: New Readily Available and Modular Ligands for Enantioselective Pd-Catalyzed Allylic Substitutions

The construction of a novel class of amino-phosphite/phosphinite/phosphine ligands containing a protected pyrrolidine-3,4-diol moiety is presented. These ligands are obtained from readily available sugars. They thus contain the advantages of carbohydrates in terms of selection of the stereogenic carbons, polyfunctional groups able to modulate the electronic and steric properties, and the general good stability of carbohydrate derivatives. They constitute a novel class of P,N-ligands that have been used in the enantioselective allylic substitutions of acyclic and cyclic substrates with varied electronic and steric requirements, using different C- and N-nucleophiles, with high enantioselectivities. Among the three groups of P,N-ligands (amino-P; P = phosphite, phosphinite, and phosphine groups) the new amino-phosphite ligands give the widest substrate and nucleophile scope, including the more challenging hindered linear and cyclic substrates. In particular, for carbohydrate-derived amino-phosphite ligands and linear substrates, high enantioselectivity in the reactions requires an R configuration of the binaphthyl moiety. However, for cyclic substrates both product enantiomers can be reached by setting out the chirality of the binaphthyl phosphite moiety. A detailed investigation of the appropriate Pd intermediates is also presented.

Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions

A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.

Asymmetric Allylic Alkylation and Hydrogenation with Transition Metal Complexes of Diphosphite Ligands Based on (1S,2S)-Trans-1,2-cyclohexanediol

Abstract: The preparation of new palladium complexes in situ that were composed of a series of chiral diphosphite ligands, which were derived from (1S,2S)-trans-1,2-cyclohexanediol, have been described. It was found that (1S,2S)-bis[(S)-1,1′-binaphthyl-2,

Chiral oxazoline NNP type ligands as well as synthesis method and application thereof

The invention relates to chiral oxazoline NNP type ligands as well as a synthesis method and an application thereof. The ligands adopt the structure shown in general formula 1 or 2. During preparation, a chiral ligand 1 and a chiral ligand 2 are prepared from Fmoc-Cl and a chiral amino acid compound 3 used as initial raw materials through multi-step reactions. The ligands can be applied to catalytic synthesis of chiral beta ketone ester fluoride and synthesis of propanedione derivatives and chiral malonate derivatives through palladium-catalyzed asymmetric allyl substitution reactions. Compared with the prior art, the reaction condition is mild, operation is easy, repeatability is good, mass preparation can be realized, and the prepared catalyst has higher ee value and yield when applied to beta ketone ester fluoridation and palladium-catalyzed asymmetric allyl substitution reactions.

Aminoalkyl-phosphine (P,N) ligands with pentane-2,4-diyl backbone in asymmetric allylic substitution reactions

Abstract: The asymmetric allylic substitution reaction of rac-1,3-diaryl-2-propenyl acetates with several C- and N-nucleophiles catalyzed by the palladium-complexes of eleven structurally analogous aminoalkyl-phosphines (P,N) with pentane-2,4-diyl backbone is reported. The role of the N-substituents and the influence of the ligand/palladium molar ratio on the activity and enantioselectivity of the catalytic system are studied. The solvent and the temperature dependence of the catalytic reaction were also assessed yielding enantioselectivities up to 95% in alkylation and 90% in amination processes under optimized reaction conditions.

Fei-Phos ligand-controlled asymmetric palladium-catalyzed allylic substitutions with structurally diverse nucleophiles: Scope and limitations

To shed light on the scope and limitations of palladium-catalyzed allylic alkylation in the presence of chiral trans-1,2-diaminocyclohexane-derived Fei-Phos as an effective phosphine ligand, the asymmetric palladium-catalysed alkylation of structurally diverse hard/soft nucleophiles, including allylic etherification of alcohols and the allylic alkylation of activated methylene compounds, indoles, and aromatic amines were investigated in this study; the corresponding products with various functional groups were achieved in good yield and with high enantioselectivity (up to 99% ee).