2732-21-0

Upstream product

• 19713-73-6 methyl (2Z)-3-phenylprop-2-enoate 
• 925-90-6 ethylmagnesium bromide 
• 103-26-4 Methyl cinnamate 
• 7719-09-7 thionyl chloride 
• 16460-78-9 (S)-3-phenylvaleric acid 
• 103-26-4 methyl cinnamate 
• 100-58-3 phenylmagnesium bromide 
• 79164-27-5 C₁₉H₂₁NO₂ 
• 174590-38-6 (4R)3-(1-oxo-2-pentenyl)-4-phenyl-2-oxazolidinone 
• 199439-32-2 (S)-3-phenylvaleryl chloride 
• 159563-72-1 (R) 2,2-dimethyl-6-(α-ethylphenethyl)-4H-1,3-dioxin-4-one 
• 162174-91-6 (S) 2,2-dimethyl-6-(α-ethylphenethyl)-4H-1,3-dioxin-4-one 
• 15790-87-1 Methyl (E)-2-pentenoate 
• 186581-53-3 diazomethane 

Downstream Products

• 95871-32-2 rac.-3-Phenyl-1,1-bis-(2-methoxy-phenyl)-pentanol-(1) 
• 2732-19-6 (+)(S)-3-Phenyl-1,1-bis-(2-methoxy-phenyl)-pentanol-(1) 

Relevant academic research and scientific papers

Cu(I) Tol-BINAP-catalyzed enantioselective Michael reactions of Grignard reagents and unsaturated esters

A highly efficient regio- and enantioselective catalytic asymmetric addition of Grignard regeants to α,β-unsaturated esters promoted by the CuI-Tol-BINAP system is described. Copyright

On the mechanism of Cu-catalyzed enantioselective extended conjugate additions: A structure-based approach

The enantioselective 1,6-addition to unsaturated carbonyl compounds offers unique opportunities to study the range of selectivities one can obtain using Cu catalysis. Here, a substrate-reagent approach to obtain structural information on the mechanism of extended conjugate additions is reported. By studying the influence of several halides in the Grignard reagent and in the Cu source on the enantioselective 1,6-addition, it was shown that it is advantageous to use a combination of EtMgBr as Grignard reagent and CuI as Cu source. Furthermore, exploring substrates bearing several alkyl esters revealed that tBu-ester substrates enhance the enantiodiscrimination in the 1,6-addition and allow the addition of BnCH2MgBr. Substrates with a variety of electron-withdrawing groups were investigated as well, identifying that ester substrates are optimal for the 1,6-addition. Two other investigations feature Me-substituted olefin substrates and substrates with all possible olefin geometries. These studies show unprecedented high enantioselectivity in the 1,6-addition when α-Me substrates are used and give relevant insight into the 1,6-addition mechanism. Finally, substrates with three or four olefins in conjugation with the electron-withdrawing groups were studied. Here, a 1,8-addition is reported that gives the corresponding products in reasonable yield, regio- and stereoselectivity. With the combined results of these studies, elucidating key substrate and reagent parameters, an adapted mechanism for the enantioselective 1,6-addition is proposed. This mechanism features the activation of a dimeric precatalyst by an equivalent of Grignard reagent, active catalyst coordination to the internal olefin of the substrate in a CuI-π-complex, followed by coordination of the catalyst to the remote olefin forming another CuI-π-complex. From the latter CuI-complex, an oxidative addition gives a CuIII-σ-complex at the δ-carbon, followed by transfer of the alkyl moiety to the δ-position. This reductive elimination yields the product and reforms the active CuI catalyst via transmetalation with another molecule of Grignard reagent.

Synthesis of new derivatives of copper complexes of Josiphos family ligands for applications in asymmetric catalysis

A series of new copper complexes containing chiral ferrocenyl diphosphine ligands of the Josiphos family have been prepared. These complexes have been studied in the catalytic asymmetric 1,2-addition of Grignard reagents to enones and aromatic ketones. Variation of the electronic and steric properties of the ligand resulted in a positive effect in the regio- and enantioselectivity of Grignard reagents to α-H-substituted enones using the ligand in which tert-butyl substituents were introduced in the diarylphosphine moiety. The copper complexes were also successfully applied in the catalytic asymmetric conjugate addition of Grignard reagents to enoates. No increase of enantioselectivity was observed in the catalytic asymmetric addition of linear Grignard reagents, compared to that of the commercially available ligand rev-Josiphos. The Royal Society of Chemistry 2014.

On the mechanism of the copper-catalyzed enantioselective 1,4-addition of Grignard reagents to α,β-unsaturated carbonyl compounds

The mechanism of the enantioselective 1,4-addition of Grignard reagents to α,β-unsaturated carbonyl compounds promoted by copper complexes of chiral ferrocenyl diphosphines is explored through kinetic, spectroscopic, and electrochemical analysis. On the basis of these studies, a structure of the active catalyst is proposed. The roles of the solvent, copper halide, and the Grignard reagent have been examined. Kinetic studies support a reductive elimination as the rate-limiting step in which the chiral catalyst, the substrate, and the Grignard reagent are involved. The thermodynamic activation parameters were determined from the temperature dependence of the reaction rate. The putative active species and the catalytic cycle of the reaction are discussed.

Copper-catalyzed enantioselective conjugate addition of Grignard reagents to α,β-unsaturated esters

(Chemical Equation Presented) Stable dinuclear Cu complexes have been used to catalyze the conjugate addition of inexpensive and readily available Grignard reagents to acyclic α,β-unsaturated esters. The method provides the correspending β-substituted optically active esters in high yields and with excellent enantioselectivities (see scheme). R3 = cyclohexyl, R 4 = Ph or R3 = Ph, R4 = cyclohexyl.

Pyran-2-ones and 5,6-dihydropyran-2-ones useful for treating hyperplasia and other diseases

Certain 2H-pyran-2-ones are useful for treating benign prostatic hypertrophy or hyperplasia, prostatic cancer, alopecia, hirsutism, acne vulgaris and seborrhea.