129646-79-3

Upstream product

• 104713-12-4 (R)-1-phenylprop-2-en-1-ol 
• 108-24-7 acetic anhydride 
• 108-05-4 vinyl acetate 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 108-59-8 malonic acid dimethyl ester 
• 108-22-5 Isopropenyl acetate 
• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 64-19-7 acetic acid 
• 100-52-7 benzaldehyde 

Downstream Products

• 164713-27-3 dimethyl 2-((R)-1-phenylallyl)malonate 
• 87802-78-6 dimethyl (S)-2-(1-phenylallyl)malonate 
• 104713-12-4 (R)-1-phenylprop-2-en-1-ol 
• 1337953-62-4 (4R,1'S)-4-methyl-2-phenyl-4-(1'-phenylallyl)oxazol-5(4H)-one 
• 1337953-65-7 (S,E)-2-(3-phenyl-2-propenyl)-4-methyl-2-phenyloxazol-5(2H)-one 

Relevant academic research and scientific papers

2: An efficient catalyst for highly regioselective allylic alkylations of chelated amino acid ester enolates

Chelated amino acid ester enolates are excellent nucleophiles for ruthenium-catalyzed allylic alkylations. Although [Cp*Ru(MeCN) 3]PF6 was found to be the most reactive catalyst investigated, with the resulting allyl complexes reacting at temperatures as low as -78°C, unfortunately the process took place with only moderate regio- and diastereoselectivity. In contrast, [(p-cymene)RuCl2]2 allowed allylations to be performed with a high degree of regioretention. Secondary allyl carboxylates with a terminal double bond were found to be the most reactive substrates, giving rise to the branched amino acids with perfect regioretention and chirality transfer. In this case, no isomerization of the Ru-allyl complex formed in situ was observed, in contrast to the analogues palladium complexes. This isomerization-free protocol can also be used for the synthesis of (Z)-configured γ,δ-unsaturated amino acid derivatives, starting from (Z)-allylic substrates. Here, the more reactive phosphates were found to be superior to the carboxylates, providing the required amino acids in almost quantitative yield with perfect regio- and stereoretention. Therefore, the Ru-catalyzed allylation reactions are well positioned to overcome the drawbacks of Pd-catalyzed processes.

Base-Free Dynamic Kinetic Resolution of Secondary Alcohols with a Ruthenium-Lipase Couple

We report the dynamic kinetic resolution (DKR) of various secondary alcohols by the combination of a ruthenium catalyst and an anionic surfactant-activated lipoprotein lipase. The DKR reactions performed under totally base-free conditions at room temperature provided the products of excellent enantiopurities (91-99% ee or greater) in high yields (92-99%). More importantly, the DKR of α-arylallyl alcohols was achieved for the first time with high yields (87-91%).

Pseudomonas sp. Lipase Immobilized on Magnetic Porous Polymer Microspheres as an Effective and Recyclable Biocatalyst for Resolution of Allylic Alcohols

Magnetic porous polymeric microspheres containing epoxy groups were prepared by suspension polymerization (denoted as magnetic Fe3O4@GEM microspheres). Fe3O4@GEM with a specific surface area of 30.41 m2/g, average pore diameter of 17.13 nm, and pore volume of 0.13 cm3/g exhibited superparamagnetic behavior with the saturation magnetization of 7.1 emu/g. The content of epoxy groups on Fe3O4@GEM was 0.22 mmol/g. Pseudomonas sp. lipase (PSL) was covalently immobilized onto the Fe3O4@GEM microspheres through the reaction between the amino groups of the enzyme and the epoxy groups on the microspheres. PSL/Fe3O4@GEM exhibited enhanced enantioselectivity for the resolution of allylic alcohol to the corresponding optically active (S)-allylic alcohol and (R)-allylic alcohol acetate compared to free PSL. The enantiomeric excess of (S)-l-pheny-2-propen-1-ol for the former (98.1%) was 81.7 times that of the latter (1.2%) when the immobilized PSL was used for transesterification resolution of (R,S)-l-pheny-2-propen-1-ol. Furthermore, the ees and eep values were still retained at 95.2% and 95.4% after PSL/Fe3O4@GEM was recycled 10 times, indicating that PSL/Fe3O4@GEM had very good reusability. In addition, the transesterification resolution of (R,S)-1-(4-methylphenyl)-2-propen-1-ol and (R,S)-1-(4-bromophenyl)-2-propen-1-ol was catalyzed by PSL/Fe3O4@GEM, affording ideal ees and eep values of 99.3%, 97.4% and 99.6%, 98.2%, respectively. Therefore, PSL/Fe3O4@GEM demonstrated its potential as a highly efficient enzymatic reactor and Fe3O4@GEM would be very promising carriers for immobilizing enzymes in industrial application.

Highly efficient kinetic resolution of allylic alcohols with terminal double bond

In this study, the lipase-catalyzed kinetic resolution (Novozyme 435) was employed to prepare chiral allylic alcohols and acetates with terminal double bonds in enantiomeric excesses ranging from 94 to >99 %.

Kinetic resolution of allylic alcohols via stereoselective acylation catalyzed by lipase PS-30

By using lipase PS-30 as catalyst, the kinetic resolution of a series of racemic allylic alcohols has been achieved via stereoselective acylation. The value of kinetic enantiomeric ratio (E) reached up to 968. Substituent effect is briefly discussed.

A new mathematical method for determining the enantiomeric ratio in lipase-catalyzed reactions

We present a new mathematical method for determining the enantiomeric ratio (E) during lipase-catalyzed kinetic resolutions. The method involves the fitting of a model to profiles of adimensionalized concentrations of the two enantiomers of the chiral substrate, plotted against degree of conversion. The model equations are presented for a reversible reaction involving bi-bi ping-pong kinetics in which the chiral substrate enters second and the chiral product leaves second. However, it is also shown that the method is easy to modify for analysis of resolutions involving other chiral substrate-product pairs and of resolutions in which the behavior of the system can be approximated by irreversible uni-uni kinetics. We show that our method retains several advantageous features of existing methods that help to ensure accuracy.

Enzymatic kinetic resolution of primary allenic alcohols. Application to the total synthesis and stereochemical assignment of striatisporolide A

Crude Porcine pancreatic lipase was successfully used for the kinetic resolution of axially chiral primary allenic alcohols providing very high enantioselectivities with E values above 200. This simple access to optically active allenes was applied to the total synthesis of the fungal metabolite (-)-striatisporolide A, allowing its unambiguous stereochemical assignment.

Synthesis of enantiopure 1-arylprop-2-en-1-ols and their tert-butyl carbonates

(Chemical Equation Presented) Enantiomerically pure 1-arylpropenols 8 have been prepared by resolution of the corresponding racemates, using the lipase formulation Novozyme 435. Deprotonation of the latter alcohols with n-BuLi, followed by derivatization with (t- BuO)2CO, afforded the corresponding carbonates 5. Optimization of the process is presented.

Iridium(I)-catalyzed stereospecific decarboxylative allylic amidation of chiral branched benzyl allyl imidodicarboxylates

(Chemical Equation Presented) Ir(I)-catalyzed decarboxylase allylic amidation of chiral branched benzyl allyl imidodicarboxylates has been shown to proceed with complete retention of enantiomeric purity and configuration. The transformation is stereospecific and appears to be quite general, accommodating a wide range of R groups.