148531-92-4Relevant articles and documents
Kinetic resolution of chiral α-olefins using optically active ansa-zirconocene polymerization catalysts
Baar, Cliff R.,Levy, Christopher J.,Min, Endy Y.-J.,Henling, Lawrence M.,Day, Michael W.,Bercaw, John E.
, p. 8216 - 8231 (2007/10/03)
A series of enantiopure C1-symmetric metallocenes, {(SiMe 2)2[η5-C5H(CHMe 2)2][η5-C5H2((S) CHMeCMe3)]}ZrCl2, (S)-2, {(SiMe2) 2[η5-C5H(CHEt2) 2][η5-C5H2((S)-CHMeCMe 3)]}ZrCl2, (S)-6, and {(SiMe2) 2[η5-C5HCy2][η5- C5H2((S)-CHMeCMe3)]}ZrCl2), (S)-7 (Cy = cyclohexyl), zirconocene dichlorides that have an enantiopure methylneopentyl substituent on the "upper" cyclopentadienyl ligand, and diastereomerically pure precatalysts, {(SiMe2) 2[η5-C5H((S)-CHMeCy)(CHMe 2)][η5-C5H3]}ZrCl2, (S)-8a and (S)-8b, which have an enantiopure, 1-cyclohexylethyl substituent on the "lower" cyclopentadienyl ligand, has been synthesized for use in the polymerization of chiral α-olefins. When activated with methylaluminoxane, these metallocenes show unprecedented activity for the polymerization of bulky racemic monomers bearing substitution at the 3- and/or 4-positions. Due to the optically pure nature of these single site catalysts, they effect kinetic resolution of racemic monomers: the polymeric product is enriched with the faster reacting enantiomer, while recovered monomer is enriched with the slower reacting enantiomer. The two components are easily separated. For most olefins surveyed, a partial kinetic resolution was achieved (s = kfaster/kslower ≈ 2), but, in one case, the polymerization of 3,4-dimethyl-1-pentene, high levels of separation were obtained (s > 15). 13C NMR spectroscopy of poly (3-methyl-1-pentene) produced with (S)-2 indicates that the polymers are highly isotactic materials. X-ray crystal structure determinations for (S)-2, {(SiMe2)2[η 5-C5H(CHMe2)2][η5- C5H2((S)-CHMeCMe3)]}Zr(SC6H 5)2, (S)-6, and (S)-7 have been used in combination with molecular mechanics calculations to examine the prevailing steric interactions expected in the diastereomeric transition states for propagation during polymerization. Precatalysts (S)-8a and (S)-8b are less selective polymerization catalysts for the kinetic resolution of 3-methyl-1-pentene than are (S)-2, (S)-6, and (S)-7.
S-ethyl thiooctanoate as acyl donor in lipase catalysed resolution of secondary alcohols
Frykman,Ohrner,Norin,Hult
, p. 1367 - 1370 (2007/10/02)
The use of S-ethyl thiooctanoate as acyl donor in resolution of secondary alcohols by lipase catalysed transesterification, resulted in an efficient displacement of the equilibrium towards esterification of the alcohol. A lipase (component B) from Candida antarctica was used as the catalyst. On a semi-preparative scale, 0.5 g of 2-octanol was resolved in less than one hour, affording an enantiomeric excess of >98% of the remaining alcohol and >97% of the produced ester. Three other alcohols, 1-phenyl ethanol, 1-cyclohexyl ethanol and trans-2-methyl cyclohexanol were also resolved with good optical yields. After 50% conversion on a preparative scale, 15 g of alcohol, the (S)-enantiomer of 2-octanol could be obtained with an enantiomeric excess of 96%. The (R)-enantiomer was isolated with an enantiomeric excess of 97% after hydrolysis of the produced ester.
