10.1002/cctc.201901543
ChemCatChem
FULL PAPER
General procedure for the deracemization of propargylic alcohol 1a
using the laccase from Trametes versicolor, TEMPO and evo-1.1-200
in analytical scale. To a solution of the corresponding racemic propargylic
alcohol 1a (0.05 mmol) in a previously oxygenated citrate buffer 50 mM pH
5.0 (2 mL) and MTBE (200 L, 10% v/v) inside a microwave tube (19 x 130
x 3 mm) open to the air, the laccase from Trametes versicolor (10 mg, 5
U) and TEMPO (2.40 mg, 0.015 mmol) were added. The mixture reacted
for 16 h with magnetic stirring at 30 °C. After this time, the following
reagents were added: iPrOH (250 L), an aqueous solution of MgCl2 (250
L, 10 mM), an aqueous solution of NADH (250 L, 10 mM), an aqueous
solution of NaOH 3 M (16.25 L) to adjust the pH to a value between 7.5
and 8.0, and evo-1.1.200 (12 mg). Then, the tube was closed and kept
under orbital shaking at 250 rpm at 30 °C for 24 h. After this time, the
mixture was extracted with EtOAc (3 x 0.5 mL), combining the organic
layers, which were dried over anhydrous Na2SO4 and filtered. Then, the
solution was concentrated and the conversion and the enantiomeric
excess values of 1a were measured by GC analyses.
Acknowledgements
Financial supports from the Spanish Ministry of Economy and
Competitiveness (MEC, Project CTQ2016-75752-R) and the
Asturian Regional Government (FC-GRUPIN-IDI/2018/000181)
are gratefully acknowledged. We thank Prof. Wolfgang Kroutil
(University of Graz, Austria) for providing us with alcohol
dehydrogenases overexpressed in E. coli cells.
Keywords: Bioreduction • Deracemization • Laccases •
Oxidation • Propargylic alcohols
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i
After this time, the following reagents were added: PrOH (788 L), an
aqueous solution of MgCl2 (1.55 mL, 10 mM), an aqueous solution of
NADH (1.55 mL, 10 mM), an aqueous solution of NaOH 3 M (113.5 L) to
adjust the pH to a value between 7.5 and 8.0, and evo-1.1.200 (80 mg).
After this time, the mixture was extracted with EtOAc (3 x 3 mL), combining
the organic layers, which were dried over anhydrous Na2SO4 and filtered.
Then, the solution was concentrated and the conversion and the
enantiomeric excess values of (R)-1a were measured by GC analyses.
The product was finally purified by column chromatography on silica gel
(30% EtOAc/Hexane), obtaining the alcohol (R)-1a in 79% isolated yield
and 98% ee.
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