868140-24-3

Upstream product

• 73930-97-9 3-acetoxy-1,3-diphenylpropene 
• 105-53-3 diethyl malonate 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 
• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 108-59-8 malonic acid dimethyl ester 
• 223438-91-3 1,3-diphenyl-2-propenyl pivalate 

Relevant academic research and scientific papers

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 Phosphoric Acid Catalyzed Atroposelective C?H Amination of Arenes

N-arylcarbazole structures are important because of their prevalence in natural products and functional OLED materials. C?H amination of arenes has been widely recognized as the most efficient approach to access these structures. Conventional strategies involving transition-metal catalysts suffer from confined substrate generality and the requirement of exogenous oxidants. Organocatalytic enantioselective C–N chiral axis construction remains elusive. Presented here is the first organocatalytic strategy for the synthesis of novel axially chiral N-arylcarbazole frameworks by the assembly of azonaphthalenes and carbazoles. This reaction accommodates broad substrate scope and gives atropisomeric N-arylcarbazoles in good yields with excellent enantiocontrol. This approach not only offers an alternative to metal-catalyzed C–N cross-coupling, but also brings about opportunities for the exploitation of structurally diverse N-aryl atropisomers and OLED materials.

Construction of C?C Axial Chirality via Asymmetric Carbene Insertion into Arene C?H Bonds

By using diazonaphthoquinones and anilines as key reagents and through a point-to-axis chiral transfer strategy, the atroposelective synthesis via asymmetric C(sp2)?H bond insertion reaction of arenes has been realized under rhodium catalysis, providing the resulting biaryl atropisomers in moderate to excellent yields with good enantiomeric ratios (up to 99:1). Further elaboration indicates this type of axially biaryl scaffold may have promising potentials in developing novel chiral ligands.

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.

An improved class of phosphite-oxazoline ligands for Pd-catalyzed allylic substitution reactions

A method for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)?1) and excellent enantioselectivities (ee's up to 99%) have been achieved for many hindered and unhindered substrates with a wide range of C-, O-, and N-nucleophiles (73 substitution products in total). Moreover, DFT and NMR studies of the key Pd-allyl complexes allowed us to better understand the origin of the excellent enantioselectivities observed experimentally. The useful application of the Pd/phosphite-oxazoline catalysts was demonstrated by the syntheses of many chiral carbobicycles, with multiples stereocenters, by simple sequential reactions involving Pd-allylic substitution and either 1,6-enyne cyclization or Pauson?Khand enyne cyclization.

A readily accessible and modular carbohydrate-derived thioether/selenoether-phosphite ligand library for Pd-catalyzed asymmetric allylic substitutions

A large library of thioether/selenoether-phosphite ligands have been tested in the Pd-catalyzed asymmetric allylic substitution reaction. The presented ligands are derived from cheap and available carbohydrates and they are air-stable solids and easy to handle. Their highly modular nature has made it possible to achieve excellent enantioselectivities in the substitution of a range of hindered and unhindered substrates (ees up to 99% and 91%, respectively). In addition, twelve C-, N- and O-nucleophiles can be efficiently introduced, independently of their nature. Among the whole library, ligands that contain an additional chiral centre in the alkyl backbone chain next to the phosphite group and an enantiopure biaryl phosphite group provided the best enantioselectivities. In general, there is a cooperative effect between these two chiral elements, and therefore, a matched combination between them is necessary to achieve the highest enantioselectivities. However, in the case of cyclic substrates, this cooperative effect is less pronounced and advantageously, both enantiomers of the product can be obtained by setting up the desired configuration of the biaryl phosphite group. Studies of the key Pd-π-allyl intermediates allowed us to better understand the enantioselectivities obtained experimentally.

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

Chiral Ferrocenyl N,N Ligands with Intramolecular Hydrogen Bonds for Highly Enantioselective Allylic Alkylations

Several new ferrocene-derived bidentate N ligands, which contain multiple chiral factors, have been designed and synthesized by a rational combination of oxazoline and pyridine. Their catalytic performances were investigated preliminarily in Pd-catalyzed

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.