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P. Hara et al. / Journal of Molecular Catalysis B: Enzymatic 67 (2010) 129–134
15/[EMIM][NTf2]/lipase PS catalysts was studied (Table 5). Based
on our earlier results [11,12], diisopropyl ether (DIPE) was chosen
as a solvent for the acylation of 2 at 25 ◦C and tert-butyl methyl
ether (TBME) for the acylation of 3 at 45 ◦C. The initial rates for 1–3
were all clearly enhanced when [EMIM][NTf2] was present in the
catalyst (compare entries 1–2, 3–4 and 5–6). The acylation of 2 pro-
ceeded to 51% conversion in 6 h with poor enantioselectivity in the
presence of ACC 507-15/[EMIM][NTf2]/lipase PS and to 46% con-
version the presence of ACC 507-15/lipase PS (entries 3 and 4). The
acylation of 3 started to retard significantly already after 4 h and
the reaction stopped at around 36% conversion. When the catalyst
was removed, clear substrate and product crystals were detected
on the surface of the catalyst explaining the inactivation. In spite
of this, the reaction proceeded with excellent enantioselectivity as
shown by E > 200 and ee > 99% for the product enantiomer (entries
5 and 6).
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Lipase PS was immobilized on active carbon coal, alumina,
ACC 507-15 active carbon cloth and STV 505 active carbon paper
with and without ionic liquids. These catalysts were evaluated
in the acylation of 1 with vinyl acetate in toluene. ACC 507-
15/[EMIM][NTf2]/lipase PS catalyst in toluene was shown to be
excellently reusable and temperature stable when the same SILE
catalyst was studied for reuse at eight temperatures over the tem-
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The same study with ACC 507-15/lipase PS catalyst showed activity
loss, indicating that [EMIM][NTf2] in the SILE activates and sta-
bilizes lipase PS. Another benefit of the catalyst is that it can be
cut into pieces with known amounts of the enzyme and the cat-
alyst can be picked up with tweezers instead of using filtration
or centrifugation. It was also shown that the catalyst in hexane
looses its activity already at 50 ◦C and that another SILE, ACC
507-15/[EMIM][BF4]/lipase PS, in toluene shows similar although
less pronounced inactivation trend with temperature. Encouraging
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also observed when the acylation of two secondary alcohols 2 and
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Acknowledgement
The work was supported by the Academy of Finland (grant
210263 to L.T.K.).
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