- Enzyme-mediated enantioselective hydrolysis of 1,2-diol monotosylate derivatives bearing an unsaturated substituent
-
We have succeeded in the easy preparation of optically active 1,2-diol monotosylates bearing an unsaturated substituent via enzymatic hydrolysis. Lipase PS quickly catalyzes the hydrolyses of 2-acetoxybut-3-enyl tosylate, which has a double bond, and 2-acetoxybut-3-ynyl tosylate, which has a triple bond, with excellent enantioselectivity to afford the corresponding optically active compounds. The reaction is also applicable to acetates with a longer chain, which has a double bond at the terminus. To demonstrate the applicability of this method, enantiomerically pure (R)-massoialactone, a natural coconut flavor, has been synthesized from racemic 2-acetoxypent-4-enyl tosylate in several steps. Furthermore, the enzyme can recognize the stereochemistry of olefins, and the (Z)-alkenyl structure is more suitable for the enantioselective hydrolysis than the (E)-isomer.
- Matsumoto,Oohana,Hashimoto,Usuda,Shimoda,Ohshima,Suzuki,Togawa
-
p. 3981 - 3988
(2018/06/15)
-
- New synthesis of sn-1,2- and sn-2,3-O-diacylglycerols application to the synthesis of enantiopure phosphonates analogous to triglycerides: A new class of inhibitors of lipases
-
Phosphonate compounds mimic the first transition state occurring during enzymatic carboxyester hydrolysis of natural substrates by forming a covalent bond with the catalytic serine. However, until now the organophosphorus compounds used in the inhibition studies more or less resembled a natural triglyceride substrate. In order to elucidate the interfacial activation and the mechanism of action of lipases, specific inhibitors need to be prepared. To achieve this goal, enantiomerically pure sn-1,2- and sn-2,3O- didecanoylglycerol compounds were prepared - starting from a C-4 chiral synthon, 3-buten-1,2-diol - and treated with n-pentylphosphonic dichloride and p-nitrophenol to afford the corresponding diastereomeric phosphonates, which were acylglycerol analogs. Subsequent separation of each of the phosphonate diastereomers A/B or ent-A/ent-B, performed by HPLC, led to four enantiopure stereoisomers that will be investigated as inhibitors of Human Pancreatic Lipase (HPL) and Human Gastric Lipase (HGL) using the monomolecular film technique.
- Marguet, Frank,Cavalier, Jean-Francois,Verger, Robert,Buono, Gerard
-
p. 1671 - 1678
(2007/10/03)
-
- Chemoenzymatic synthesis of enantiomerically pure alkene 1,2-diols and glycosides thereof
-
The kinetic resolution of racemic 2-O-acylated 3-butene-1,2-diol and 1- O-acylated 3-butene-1,2-diol derivatives by enzymatic saponification and enzymatic esterification, respectively, is investigated with several lipases and esterases. The resulting part
- Ziegler, Thomas,Bien, Frank,Jurisch, Claus
-
p. 765 - 780
(2007/10/03)
-