136892-39-2

Upstream product

• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 108-59-8 malonic acid dimethyl ester 
• 74-88-4 methyl iodide 
• 609-02-9 methyl-malonic acid dimethylester 
• 62116-54-5 dimethyl methylmalonate sodium salt 
• 121440-71-9 ethyl (E)-1,3-diphenyl-2-propen-1-yl carbonate 
• 614-47-1 1,3-diphenyl-propen-3-one 
• 62668-02-4 (E)-1,3-diphenyl-2-propen-1-ol 
• 73930-97-9 3-acetoxy-1,3-diphenylpropene 
• 121440-72-0 (E)-1,3-diphenylallyl methyl carbonate 
• 252027-83-1 trans-3-benzoyl-1,3-diphenyl-1-propene 

Relevant academic research and scientific papers

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.

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.

Synthetic and mechanistic studies in enantioselective allylic substitutions catalysed by palladium complexes of a modular class of axially chiral quinazoline-containing ligands

The application of palladium complexes of a modular series of axially chiral phosphinamine ligands, the Quinazolinaps, to the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and methyl dimethyl malonate is described.

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.

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.

A d -Camphor-Based Schiff Base as a Highly Efficient N,P Ligand for Enantioselective Palladium-Catalyzed Allylic Substitutions

New Schiff bases derived from chiral d-camphor were determined to be effective phosphine ligands for the asymmetric palladium-catalyzed allylic alkylation of activated methylene compounds, the allylic etherification of alcohols, and the allylic amination of primary amines or secondary amines, in which the corresponding products with various functional groups were achieved in good yields with excellent enantioselectivities (up to >99 % ee). Remarkably, the palladium catalyst derived from Schiff base L2 afforded the highest level of enantioselectivity reported to date for allylic substitution reactions, including allylic etherification and allylic amination, which revealed the privileged role of d-camphor-derived Schiff bases in palladium-catalyzed allylic substitution reactions.

Conformational Preferences of a Tropos Biphenyl Phosphinooxazoline-a Ligand with Wide Substrate Scope

Excellent enantioselectivities are observed in palladium-catalyzed allylic substitutions of a wide range of substrate types and nucleophiles using a bidentate ligand composed of oxazoline and chirally flexible biaryl phosphite elements. This unusually wid

Asymmetric catalyzed allylic substitution using a Pd/P-S catalyst library with exceptional high substrate and nucleophile versatility: DFT and Pd-π-allyl key intermediates studies

A large library of furanoside phosphite/phosphinite/phosphine-thioether ligands L1-L17a-l has been applied in the Pd-catalyzed allylic substitution reactions of several substrate types using a wide range of nucleophiles. These ligands, which are prepared from inexpensive d-xylose, also incorporate the advantages of the heterodonor, the robustness of the thioether moiety, and the extra control provided by the flexibility of the chiral pocket through the presence of a biaryl phosphite group and a modular sugar backbone. By selecting the ligand components, we have been able to identify catalytic systems that can create new C-C, C-N, and C-O bonds in several substrate types (hindered and unhindered) using a wide range of nucleophiles in high yields and enantioselectivities (ee's up to >99%). Of particular note are the excellent enantioselectivities obtained in the etherification of linear and cyclic substrates, which represent the first example of successful etherification of both substrate types. The DFT computational study is in agreement with an early transition state. Further studies on the Pd-π-allyl intermediates provided a deep understanding of the effect of ligand structure in the origin of enantioselectivity.

New phosphine-imine ligands derived from D-gluco- and D-galactosamine in Pd-catalysed asymmetric allylic alkylation

New phosphine-imine chiral ligands which were easily prepared from D-gluco- and D-galactosamine 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.

Theoretical and Experimental Optimization of a New Amino Phosphite Ligand Library for Asymmetric Palladium-Catalyzed Allylic Substitution

A new library of modular amino phosphite ligands obtained in a few synthetic steps from enantiopure amino alcohols has been tested in asymmetric Pd-catalyzed allylic substitution. The modular ligand design is crucial to find highly selective catalysts for each substrate type using a wide range of C-, N-, and O-nucleophiles. A DFT study of the species responsible for the enantiocontrol was used to optimize the ligand structure. By selecting the ligand components, we were able to identify unprecedented catalytic systems that can create new chiral C-C, C-N, and C-O bonds in a variety of substrate types (hindered and unhindered) in high yields and enantioselectivities (ee values up to 99 %). Further studies on the Pd-π-allyl intermediates provided a deep understanding of the effect of ligand structure in the origin of enantioselectivity. Potential applications of the new Pd/amino phosphite catalysts were demonstrated by the practical synthesis of a range of chiral carbocycles by simple tandem reactions, with no loss of enantioselectivity.