Enantio-selective preparation of (S)-1-phenylethanol by a novel marine GDSL lipase MT6 with reverse stereo-selectivity

We previously functionally characterized a novel marine microbial GDSL lipase MT6 and identified that the stereo-selectivity of MT6 was opposite to that of other common lipases in trans-esterification reactions.Herein,we have investigated the use of MT6 in stereo-selective biocatalysis through direct hydrolysis reactions.Notably,the stereo-selectivity of MT6 was also demonstrated to be opposite to that of other common lipases in hydrolysis reactions.Parameters,including temperature,organic co-solvents,pH,ionic strength,catalyst loading,substrate concentration,and reaction time,affecting the enzymatic resolution of racemic 1-phenylethyl acetate were further investigated,with the e.e.of the final（S）-l-Phenylethanol product and the conversion being 97%and 28.5%,respectively,after process optimization.The lengths of side chains of 1-phenylethyl esters greatly affected the stereo-selectivity and conversion during kinetic resolutions.MT6 is a novel marine microbial GDSL lipase exhibiting opposite stereo-selectivities than other common lipases in both trans-esterification reactions and hydrolysis reactions.

Stereo-Selective Synthesis of 5-Norbornene-2-<i>exo</i>-carboxylic Acid—Rapid Isomerization and Kinetically Selective Hydrolysis

Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.

Regio-and Stereo-selective Bioreduction of Diketo-n-butylphosphonate by Baker's Yeast

A regio- and stereo-selective reduction of diketo-n-butylphosphonates by baker's yeast was reported. The chemical yield and ee value of these reactions are highly dependent on the structure of substrates. The resulting optical active hydroxy^alkanephosphonates can be used as chirons for the synthesis of polyfunctional organophosphorus compounds. As useful building block, a series of α,β-unsaturated ketones bearing chiral hydroxy group in addition to trifluoromethyl moiety was prepared via the Horner-Wadsworth-Emmons (HWE) reaction of the biotransformation products.

Facile and Effective Synthesis of Glucopyranosyl Oligosacchardes with Alternative (1→3)-α- and -β-Linkages in the Presence of C-2 Ester Capable of Neighboring Group Participation

Coupling of acetylated α-(1→3)-linked glucobiosyl trichloro-acetimidate with acetylated α-(1→3)-linked glucobioside acceptor gave a β-linked tetrasaccharide, while coupling of acetylated β-(1→3)-linked glucobiosyl trichloroacetimidate with acetylated β-(1→3)-linked glucobioside acceptor gave an α-linked tetrasaccharide in spite of the C-2 neighboring group participation. Two hexasaccharides with alternative (1→3)-α- and -β-linkges were synthesized by these reactions via remote control exerted by the glycosylation bond in either donor or acceptor.