297179-04-5

Upstream product

• 87751-69-7 rac-(E)-1,3-diphenyl-3-acetoxy-prop-1-ene 
• 108-24-7 acetic anhydride 
• 136981-81-2 (R)-(E)-1,3-diphenyl-prop-2-en-1-ol 
• 105-53-3 diethyl malonate 
• 108-59-8 malonic acid dimethyl ester 

Downstream Products

• 1312602-64-4 (4R,5R)-5-((S)-hydroxy(phenyl)methyl)-1-methyl-4-phenyl-pyrrolidin-2-one 
• 1448603-01-7 (R)-N-methyl-3-phenyl-3-((2S,3S)-3-phenyloxiran-2-yl)propanamide 
• 1448603-02-8 (4R,5R,6S)-5-bromo-4,6-diphenyltetrahydropyran-2-one 
• 137134-65-7 (-)-(S,E)-3,5-diphenylpent-4-enoic acid 
• 95071-02-6 dimethyl 2-[(E)-(S)-1,3-diphenylallyl]-malonate 
• 95071-02-6 (R)-methyl 2-carbomethoxy-3,5-diphenylpent-4-enoate 
• 121440-87-7 (-)-(R,E)-N-benzyl-(1,3-diphenyl-2-propenyl)amine 
• 121440-87-7 (+)-(S,E)-N-benzyl-(1,3-diphenyl-2-propenyl)amine 

Relevant academic research and scientific papers

Novel concise synthesis of (-)-clausenamide

A six-step synthesis of (-)-clausenamide is described. Optically pure (R,E)-1,3-diphenylallylic alcohol was acetylated and then subjected to an Ireland-Claisen rearrangement, giving the γ,δ-unsaturated acid, which underwent a substrate-induced stereoselective bromolactonization to afford the expected all-equatorial substituted bromo-δ-lactone. An unusual chemo-selective aminolysis of the lactone resulted in the formation of a γ,δ-epoxy-amide in stereospecific manner. Base-promoted cyclization of this intermediate and the subsequent Davis oxidation furnished the synthesis, delivering the final product in >99% ee and up to 34% overall yield. Copyright

Kinetic resolution of allylic esters in palladium-catalyzed asymmetric allylic alkylations using C-N bond axially chiral aminophosphine ligands

Chiral allylic esters, such as (R)-1,3-diphenyl-2-propenyl acetate (R)-2a, were synthesized by kinetic resolution in a palladium-catalyzed asymmetric allylic alkylation using N-aryl indoline type C-N bond axially chiral aminophosphines (S)-1 as ligands.

Palladium catalytic species containing chiral phosphites: Towards a discrimination between molecular and colloidal catalysts

Palladium nanoparticles (Pd1-Pd3) stabilized by chiral diphosphite ligands (1-3), were synthesized and tested as catalysts for the allylic alkylation reaction, using different substrates (rac-I, rac-III and rac-V). Carbohydrate ligands (1 and 2), only differing in the C-3 configuration, led to a remarkable difference in stability of the corresponding nanoparticles: while Pd1 is a robust catalyst, Pd2 decomposes into molecular species. In addition, the high enantioselective systems, Pd1 and Pd3, are only active for a substrate containing phenyl groups. Concerning the catalytic behaviour of the corresponding molecular systems, palladium complexes coordinated to ligands 1 or 3, gave excellent asymmetric inductions, but an analogous catalyst accommodating ligand 2, was not found selective.

A Case for Enantioselective Allylic Alkylation Catalyzed by Palladium Nanoparticles

Palladium nanoparticles (4 nm, fcc) were prepared through decomposition of [Pd2(dba)3] by H2 in the presence of a chiral xylofuranoside diphosphite. These particles catalyze the allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate leading to an almost total conversion of the (R) enantiomer and almost no reaction with the (S). This gives rise to 97% ee for the alkylation product and a kinetic resolution of the substrate recovered with ca. 90% ee. This behavior was compared to that of a molecular catalyst at various dilutions, and the differences between the two systems are discussed. This is the first colloidal system shown to display such a high enantioselectivity besides the well-known Pt/cinchonidine system. Copyright

Kinetic resolution in palladium-catalyzed asymmetric allylic alkylations by a P,O ligand system.

[reaction: see text] Through the investigation of peptide-based phosphine oxazoline ligands, a simple P,O ligand system was developed. This system provides palladium complexes that are capable of a very high degree of kinetic resolution of 1,3-diphenylpro

Kinetic resolution in Pd-catalyzed allylic substitution using the helical PHelix ligand

The chiral helical diphosphine 2,15-bis(diphenylphosphino)-hexahelicene (PHelix) is an excellent ligand in palladium catalyzed kinetic resolution involving allylic substitution. Depending upon the substrate, enantioselectivities (ee) of up to 99% are observed. Although formally a diphosphine, PHelix appears not to undergo chelation, which means that it behaves as a chiral monophosphine.

Pd-catalyzed asymmetric synthesis of allylic tert-butyl sulfones and sulfides: Kinetic resolution of the allylic substrate by a chiral Pd-complex

The acyclic and cyclic allylic tert-butyl sulfones 3, ent-3, 11a, 11b and 15a-c of 89-98% ee were synthesized in 40-92% yield by a Pd-catalyzed reaction of the respective allylic acetates and carbonates rac-1a, rac-1b, rac-10a, rac-10b and rac-14a-c with