140630-34-8

Upstream product

• 876-27-7 4-chlorophenyl acetate 
• 4769-73-7 (RS)-1-chloro-3-phenyloxy-2-propanol 
• 108-05-4 vinyl acetate 
• 108-22-5 Isopropenyl acetate 
• 538-43-2 3-phenoxy-1,2-propanediol 

Downstream Products

• 133522-40-4 (R)-(-)-1-amino-3-phenyloxy-2-propanol 
• 140630-43-9 (2R)-1-Isopropylamino-3-phenoxy-2-propanol 
• 71031-03-3 (2R)-1,2-epoxy-3-phenoxypropane 

Relevant academic research and scientific papers

Ionic liquid-coated enzyme for biocatalysis in organic solvent

Ionic liquid-coated enzyme (ILCE) is described as a useful catalyst for biocatalysis in organic solvent. An ionic liquid, [PPMIM]-[PF6] (1, [PPMIM] = 1-(3′-phenylpropyl)-3-methylimidazolium), which is solid at room temperature and becomes liquid above 53°C, was synthesized in two steps from N-methylimidazole. The coating of enzyme was done by simply mixing commercially available enzyme with 1 in the liquid phase above 53°C and then allowing the mixture to cool. A representative ILCE, prepared with a lipase from Pseudomonas cepacia, showed markedly enhanced enantioselectivity without losing any significant activity.

Highly efficient route for enantioselective preparation of chlorohydrins via dynamic kinetic resolution

(Equation Presented) Dynamic kinetic resolution (DKR) of various aromatic chlorohydrins with the use of Pseudomonas cepacia lipase (PS-C "Amano" II) and ruthenium catalyst 1 afforded chlorohydrin acetates in high yields and high enantiomeric excesses. These optically pure chlorohydrin acetates are useful synthetic intermediates and can be transformed to a range of important chiral compounds.

Aminocyclopentadienyl Ruthenium Complexes as Racemization Catalysts for Dynamic Kinetic Resolution of Secondary Alcohols at Ambient Temperature

Aminocyclopentadienyl ruthenium complexes, which can be used as room-temperature racemization catalysts with lipases in the dynamic kinetic resolution (DKR) of secondary alcohols, were synthesized from cyclopenta-2,4-dienimines, Ru3(CO)12, and CHCl 3: [2,3,4,5-Ph4(η5-C 4CNHR)]Ru-(CO)2Cl (4: R = i-Pr; 5: R = n-Pr; 6: R = t-Bu), [2,5-Me2-3,4-Ph2(η5-C 4CNHR)]Ru(CO)2Cl (7: R = i-Pr; 8: R = Ph), and [2,3,4,5-Ph4(η5-C4CNHAr)]Ru(CO) 2Cl (9: Ar =p-NO2C6H4; 10: Ar = p-ClC6H4; 11: Ar = Ph; 12: Ar = p-OMeC6H 4; 13: Ar = p-NMe2C6H4). The tests in the racemization of (S)-4-phenyl-2-butanol showed that 7 is the most active catalyst, although the difference decreased in the DKR. Complex 4 was used in the DKR of various alcohols; at room temperature, not only simple alcohols but also functionalized ones such as allylic alcohols, alkynyl alcohols, diols, hydroxyl esters, and chlorohydrins were successfully transformed to chiral acetates. In mechanistic studies for the catalytic racemization, ruthenium hydride 14 appeared to be a key species. It was the major organometallic species in the racemization of (S)-1-phenylethanol with 4 and potassium tert-butoxide. In a separate experiment, (S)-1-phenylethanol was racemized catalytically by 14 in the presence of acetophenone.

Chemoenzymatic dynamic kinetic resolution of β-halo alcohols. An efficient route to chiral epoxides

Enzymatic resolution of β-chloro alcohols in combination with ruthenium-catalyzed alcohol isomerization led to a successful dynamic kinetic resolution (conversion up to 99% and ee up to 97%). The efficiency of the DKR is dramatically reduced when β-bromo alcohols are used. The presence of the bromo substituent causes decomposition of the ruthenium catalysts, which triggers the progressive deactivation of the enzyme. The synthetic utility of this procedure has been illustrated by the practical synthesis of different chiral epoxides.

Water content influences the selectivity of CALB-catalyzed kinetic resolution of phenoxymethyl-substituted secondary alcohols

Derivatives of 1-phenoxy-2-alkanols were kinetically resolved by esterification with irreversible and reversible acyl donors using lipase B from Candida antarctica (Novozyme 435) as a catalyst. To optimize the relative rate of reaction (the E-value), esterifications in eight different solvents with different water activities were performed. For 3-bromo-1-phenoxy-2-propanol (1), the E-values in all the solvents were higher when the water activity was increased, while the E-values for 1-phenoxy-2-pentanol (2) and 3-chloro-1-phenoxy-2-propanol (3) decreased by increasing water activity. The water content of the various reaction media with the same water activity was determined. Solvents such as 1,4-dioxane, acetonitrile, and tetrahydrofuran contained much more water than hexane, carbon tetrachloride, cyclohexane, toluene, and benzene. At high-water activity, the high-water content of the former group of solvents resulted in termination of the reaction at low conversion. The reason seemed to be that the acyl donor and possibly also the produced esters were hydrolyzed. This was not the case when the esterification was performed in water-immiscible solvents with the same water activity.

Ruthenium- and enzyme-catalyzed dynamic kinetic resolution of secondary alcohols

Enzymatic resolution of secondary alcohols under substrate racemizing conditions was studied using an immobilized lipase from Candida antarctica in the presence of a ruthenium catalyst. A specifically designed acyl donor, 4- chlorophenyl acetate, was found to be compatible with both catalysts and resulted in an efficient dynamic kinetic resolution. Studies of the reaction in different solvents showed that nonpolar solvents gave the best results. With this process, a variety of racemic secondary alcohols were transformed to the corresponding enantiomerically pure acetates, making efficient use of all starting material. In most cases, the reaction proceeded with >99% ee and in good yield.

The efficient resolution of protected diols and hydroxy aldehydes by lipases: Steric auxilliary approach and synthetic applications

1,n-Diols (n = 2-5) and 2-hydroxy aldehydes protected with a steric auxilliary are transformed by Pseudomonas lipases with high enantioselectivity, thus allowing the efficient resolution of these molecules and the synthesis of related derivatives with high optical purity.

Enzyme Assisted Preparation of Enantiomerically Pure β-Adrenergic Blockers III. Optically Active Chlorohydrin Derivatives and Their Conversion

Optical active chlorohydrin derivatives 2a-m and 3a-m of both enantiomeric series were prepared via both enzymatic hydrolyses and acyltransfer reactions catalysed by a highly selective lipase from Pseudomonas sp..The resulting building blocks were further transformed into the corresponding β-blockers of high enantiomeric purity.