161372-07-2

Upstream product

• 39128-78-4 rac-1,1,-diphenyl-1-buten-3-yl acetate 
• 18424-76-5 dimethyl malonate sodium salt 
• 108-59-8 malonic acid dimethyl ester 
• 21711-87-5 rac-1,3,3-triphenylprop-2-enyl acetate 

Downstream Products

• 180964-67-4 ((S)-2-Methyl-4,4-diphenyl-but-3-enyl)-carbamic acid tert-butyl ester 
• 180964-63-0 3-Methyl-5,5-diphenylpent-4-enoic acid 
• 180964-61-8 Methyl 3-methyl-5,5-diphenylpent-4-enoate 

Relevant academic research and scientific papers

Palladium Catalysed Allylic Substitution Reactions of Prochiral and Racemic Allyl Acetates

The palladium catalysed reaction between non-symmetrical allyl acetates and sodiodimethylmalonate proceeds in high yields and enantioselectivities (up to 99percent ee) using a diphenylphosphinoaryl oxazoline ligand.

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

A new modular phosphite-pyridine ligand library for asymmetric Pd-catalyzed allylic substitution reactions: A study of the key Pd-π-allyl intermediates

A library of phosphite-pyridine ligands L1-L12 a-g has been successfully applied for the first time in the Pd-catalyzed allylic substitution reactions of several di- and trisubstituted substrates by using a wide range of C, N and O nucleophiles, among which are the little studied α-substituted malonates, β-diketones, and alkyl alcohols. The highly modular nature of this ligand library enables the substituents/configuration at the ligand backbone, and the substituents/configurations at the biaryl phosphite moiety to be easily and systematically varied. We found that the introduction of an enantiopure biaryl phosphite moiety played an essential role in increasing the versatility of the Pd-catalytic systems. Enantioselectivities were therefore high for several hindered and unhindered di- and trisubstituted substrates by using a wide range of C, N and O nucleophiles. Of particular note were the high enantioselectivities (up to>99 % ee) and high activities obtained for the trisubstituted substrates S6 and S7, which compare favorably with the best that have been reported in the literature. We have also extended the use of these new catalytic systems in alternative environmentally friendly solvents such as propylene carbonate and ionic liquids. Studies on the Pd-π-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity. A library of phosphite-pyridine ligands has been successfully applied in the Pd-catalyzed allylic substitution reactions of several di- and trisubstituted substrates by using a wide range of C, N, and O nucleophiles. By carefully selecting the ligand components, high regio- and enantioselectivities (up to >99 % ee) and good activities have been achieved (see scheme). The NMR studies on the Pd-π-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity. Copyright

Phosphinite thioethers derived from chiral epoxides. Modular P, S -ligands for pd-catalyzed asymmetric allylic substitutions

A new family of modular P,S-ligands has been prepared from enantiopure arylglycidols. These ligands have been iteratively optimized with respect to four different structural parameters for use in Pd-catalyzed allylic substitutions. As a final output, highly active and enantioselective ligands for these synthetically important transformations have been developed, and the factors controlling their catalytic behavior have been rationalized. From a methodological point of view, a convenient procedure for the regioselective ring-opening of cis-glycidic esters with bulky thiols to yield the corresponding β-alkylthio-α-hydroxy carboxylic acids has been developed.

A new class of modular P,N-ligand library for asymmetric Pd-catalyzed allylic substitution reactions: A study of the key Pd-π- allyl intermediates

A new class of modular P,N-ligand libary has been Synthesized and screened in the pd-catalyzed allylic substitution reaction of several substrate types. These series of ligands can be prepared efficiently from easily accessible hydroxyle - oxazale/ thiazale de-rivatives. modular nature enables the bridge, the substituents at teh hetro cyclic ring and in the alkyl back bone chain, the configuration of the ligand backbone, and the substituents/configurations in the biaryl phosphite moiety to be easily and systematically varied. By carefully selecting the ligand components, therefore, high regio- and enantioselectivities (ee values up to 96%) and good activities are achieved in a broad range of mono-, di-, and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR spectroscopic and DFT studies on the Pdπ-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity.

Highly modular P-OP ligands in asymmetric allylic substitution

A library of highly modular P-OP ligands have been evaluated in Pd-catalysed allylic substitutions with C- and N-nucleophiles. Catalyst optimisation via a variation of the phosphino and phosphite substituents led to a 'lead' catalyst, which efficiently me

Pyranoside phosphite-oxazoline ligand library: Highly efficient modular P,N ligands for palladium-catalyzed allylic substitution reactions. A study of the key palladium allyl intermediates

We have screened a library of modular phosphite-oxazoline ligands for asymmetric allylic substitution reactions. The library is efficiently prepared from the commercially available and cheap dglucosamine. The introduction of a phosphite moiety into the ligand design is highly advantageous for the product outcome. Therefore, this ligand library affords good-to-excellent reaction rates [TOFs up to 600 mol substrate × (mol Pd × h)-1] and enantioselectivities (ees up to 99%) and, at the same time, shows a broad scope for mono-, di-and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR studies on the palladium allyl intermediates provide a deeper understanding about the effect of the ligand parameters on the origin of enantioselectivity.

Phosphinooxazolines derived from 3-amino-1,2-diols: Highly efficient modular P-N ligands

A family of chiral phosphinooxazolines (12a-e) derived from modular, enantiopure β-amino alcohols has been prepared, and their palladium complexes have been used as chiral mediators in the asymmetric allylic alkylation reaction. The oxazoline moiety in 12 contains a C-4 aryl and a C-5 alkoxymethyl substituent that can be independently optimized for high catalytic activity and enantioselectivity. A methoxymethyl substituent at C-5 has beenfound to provide the best results in terms of enantioselectivity and activity in the alkylation of a diverse family of allylic substrates under both thermal and microwave-assisted activation. The palladium-phos- phinooxazoline complexes described in this work are remarkably robust, as the enantioselectivity recorded in the asymmetric allylic alkylation remains essentially unchanged in the temperature range between 20 and 130°C. An unprecedented reversal in enantioselectivity has been observed between 1, 3-diphe-nylallyl and 1,3-dimethylallyl alkylation substrates, and the origin of this behavior has beeh explained by means of ONIOM QM/MM calculations.

Application of chiral mixed phosphorus/sulfur ligands to palladium-catalyzed allylic substitutions

A modular approach to the synthesis of a class of mixed phosphorus/sulfur ligands was designed to identify important ligand structural features for enantioselective palladium-catalyzed allylic subsitutions of acyclic and cyclic ayllic esters. After a systematic variation of the ligand substituents at sulfur, phosphorus, and the ligand backbone, ligand 11k was found to be optimal in the palladium-catalyzed allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate or benzylamine in high yield and excellent enantioselectivity (95-98% ee). A similar optimization of the mixed phosphorus/sulfur ligand for the palladium-catalyzed allylic substitution of cycloalkenyl acetates showed that 49g afforded the highest enantioselectivities (91-97% ee). Application of this methodology to heterocyclic substrates was developed as an efficient approach to the enantioselective synthesis of 3-substituted piperidines and dihydrothiopyrans. Models for asymmetric induction are discussed based on the absolute stereochemistry of the products, X-ray crystallographic data, and NMR spectroscopic data for relevant π-allyl complexes.

Enantioselective palladium-catalyzed allylic alkylation using E- and Z-vinylogous sulfonates

(matrix presented). The E- and Z-vinylogous sulfonates of β-phenylcinnamyl alcohol derivatives 1 and 2 undergo rapid and enantioselective palladium-catalyzed allylic alkylation (≥90% ee) with the palladium complex of the phosphino-1,3-oxazine 3 and sodium