A rule to predict which enantiomer of a secondary alcohol reacts faster in reactions catalyzed by cholesterol esterase, lipase from Pseudomonas cepacia, and lipase from Candida rugosa

A Molecular Mechanism of Enantiorecognition of Tertiary Alcohols by Carboxylesterases

“…by switching from L-to D-tartrate in the Sharpless-epoxidation [39] by a simple and general rule. [16,17] Changes of enantiopreference by point mutations in the substrate binding site have also been observed for lipases, [15] phosphotriesterases, [41] lactate dehydrogenases, [42] and alcohol dehydrogenases. [43] Thus, our results support the general idea that enantiopreference is not an inherent property of an enzyme but can be tuned by protein engineering.…”

“…This made it possible to understand the structural basis of an empirical rule for predicting the enantiopreference towards esters of secondary alcohols from the structure of the substrate only. [16,17] However, for other substrates like small primary alcohols and triacylglycerols such an universal rule for all lipases is not applicable. [18] In general, enantiopreference depends on the details of the structure of both, the substrate and the enzyme.…”

Investigation of the Impact of Water on the Enantioselectivity Displayed by CALB in the Kinetic Resolution of δ‐Functionalized Alkan‐2‐ol Derivatives

“…For CALB the (R)-enantiomer will be preferred when the large group has a higher priority according to the CIP rule ( Figure 1). [5] Enantioselectivity is mainly quantified by the enantiomeric ratio E, which is the ratio of the rate of the R-and S-enantiomer. [6] The catalytic mechanism of lipases is built up by the residues of three amino acids: a nucleophilic serine, a histidine, and either an aspartate or a glutamate.…”

“…The preferred enantiomer in a lipase catalyzed transesterification or hydrolysis involving sec-alcohols and sec-acetate can be predicted by Kazlauskas´ rule. [5] Interestingly, for the reverse reaction, the esterification, including transesterification, the rate limiting step is the formation of the very same tetrahedral intermediate. Also in this reaction it has been shown that the selectivity of the reaction can be rationalized as the difference in energy between the TI of the R and S substrate.…”

Chemoenzymatic Synthesis of (+)-.ALPHA.-Polypodatetraene and Methyl (5R,10R,13R)-Labda-8-en-15-oate

“…The enantiopreference toward secondary alcohols by lipase from Candida rugosa has established a simple empirical rule. 12,13) Most lipases indicate low enantioselectivity toward primary alcohols. Only lipase from Pseudomonas cepacia (PCL) and lipase from porcine pancreas (PPL) show moderate to high enantioselectivity toward a wide range of primary alcohols, but even for these the enantioselectivity is usually lower than toward secondary alcohols.…”