COMMUNICATIONS
Deracemization of Amino Acids by Coupling Transaminases
0
.1N HCl (100 mL) and water (100 mL), and then was
Rodrꢄguez-Vico, F. J. L. Heras-Vꢂzquez, Recent Pat.
Biotechnol. 2008, 2, 35–46; c) A. S. Bommarius, M.
Schwarm, K. Drauz, Chimia 2001, 55, 50–59; d) L.
Krieg, M. B. Ansorge-Schumacher, M. R. Kula, Adv.
Synth. Catal. 2002, 344, 965–973.
eluted with 10% ammonia solution (150 mL). The elution
fractions were pooled and evaporated at 308C and 0.1 bar.
The resulting solids were washed with EtOH (30 mL) and
then oven-dried overnight.
[
[
6] a) S. Servi, D. Tessaro, G. Pedrocchi-Fantoni, Coord.
Chem. Rev. 2008, 252, 715–726; b) N. J. Turner, Curr.
Opin. Chem. Biol. 2010, 14, 115–121; c) C. C. Gruber, I.
Lavandera, K. Faber, W. Kroutil, Adv. Synth. Catal.
Analytical Methods
All the HPLC analyses were performed on a Waters HPLC
system (Milford, MA, USA). Keto acids were analyzed
using an Aminex HPX-87H column (Bio-Rad, Hercules,
CA, USA) with isocratic elution of 5 mM H SO solution at
2
1
006, 348, 1789–1805; d) H. Stecher, K. Faber, Synthesis
997, 1–16.
2
4
7] a) G. Shin, S. Mathew, M. Shon, B.-G. Kim, H. Yun,
Chem. Commun. 2013, 49, 8629–8631; b) D. Ghislieri,
N. Turner, Top. Catal. 2014, 57, 284–300; c) M. Hçhne,
U. T. Bornscheuer, ChemCatChem 2009, 1, 42–51; d) D.
Koszelewski, B. Grischek, S. M. Glueck, W. Kroutil, K.
Faber, Chem. Eur. J. 2011, 17, 378–383; e) R. C. Simon,
N. Richter, E. Busto, W. Kroutil, ACS Catal. 2014, 4,
À1
0
.5 mLmin . Column oven temperature was set to 408C
and UV detection was done at 210 nm. Retention times of
keto acids were 11.3 (2a), 12.0 (2b), 9.8 (2c), 14.2 (2e), 17.7
(
2f), 15.3 (2g), 10.0 (2h), 14.7 (2i) and 21.0 min (2j).
Analysis of acetophenone was performed using a Symme-
try column C18 (Waters Co.) with isocratic elution of 60%
methanol/40%
water/0.1%
trifluoroacetic
acid
at
1
29–143.
À1
1
mLmin . UV detection was done at 254 nm. Retention
[
8] A. Caligiuri, P. D’Arrigo, E. Rosini, D. Tessaro, G.
time of acetophenone was 3.8 min.
For quantitative chiral analysis of amino acids, 1-fluoro-
Molla, S. Servi, L. Pollegioni, Adv. Synth. Catal. 2006,
3
48, 2183–2190.
2,4-dinitrophenyl-5-l-alanine amide (Marfeyꢁs reagent) was
[23]
[9] Y. M. Seo, S. Mathew, H. S. Bea, Y. H. Khang, S. H.
used for amino acid derivatization. Details of the chiral
HPLC analysis are provided in the Supporting Information.
Lee, B. G. Kim, H. Yun, Org. Biomol. Chem. 2012, 10,
2
482–2485.
10] E. S. Park, J. Y. Dong, J. S. Shin, ChemCatChem 2013,
, 3538–3542.
11] K. Yonaha, H. Misono, T. Yamamoto, K. Soda, J. Biol.
Chem. 1975, 250, 6983–6989.
[
[
[
5
Acknowledgements
12] a) J. S. Shin, B. G. Kim, Biotechnol. Bioeng. 1998, 60,
This work was supported by the Advanced Biomass R&D
Center (ABC-2011-0031358) through the National Research
Foundation of Korea funded by the Ministry of Education,
Science and Technology.
5
34–540; b) E. S. Park, M. S. Malik, J. Y. Dong, J. S.
Shin, ChemCatChem 2013, 5, 1734–1738.
[
13] a) C. K. Savile, J. M. Janey, E. C. Mundorff, J. C.
Moore, S. Tam, W. R. Jarvis, J. C. Colbeck, A. Krebber,
F. J. Fleitz, J. Brands, P. N. Devine, G. W. Huisman,
G. J. Hughes, Science 2010, 329, 305–309; b) F. G.
Mutti, C. S. Fuchs, D. Pressnitz, J. H. Sattler, W. Krou-
til, Adv. Synth. Catal. 2011, 353, 3227–3233; c) K. E.
Cassimjee, C. Branneby, V. Abedi, A. Wells, P. Ber-
glund, Chem. Commun. 2010, 46, 5569–5571.
References
[1] a) R. Patel, Biomolecules 2013, 3, 741–777; b) V. Gotor-
Fernꢂndez, V. Gotor, Curr. Opin. Drug Discovery Dev.
2
009, 12, 784–797; c) M. Breuer, K. Ditrich, T. Habich-
[
[
14] K. Hirotsu, M. Goto, A. Okamoto, I. Miyahara, Chem.
er, B. Hauer, M. Kesseler, R. Sturmer, T. Zelinski,
Angew. Chem. 2004, 116, 806–843; Angew. Chem. Int.
Ed. 2004, 43, 788–824.
Rec. 2005, 5, 160–172.
15] M. J. Berna, J. A. Tapia, V. Sancho, R. T. Jensen, Curr.
Opin. Pharmacol. 2007, 7, 583–592.
16] M. Sasa, J. Pharmacol. Sci. 2006, 100, 487–494.
[2] a) L. D. Tran, O. Daugulis, Angew. Chem. 2012, 124,
[
[
5
278–5281; Angew. Chem. Int. Ed. 2012, 51, 5188–5191;
17] W. A. Nugent, J. E. Feaster, Synth. Commun. 1998, 28,
b) S. J. Zuend, M. P. Coughlin, M. P. Lalonde, E. N. Ja-
1
617–1623.
cobsen, Nature 2009, 461, 968–970.
3] W. Leuchtenberger, K. Huthmacher, K. Drauz, Appl.
Microbiol. Biotechnol. 2005, 69, 1–8.
[
[
18] E. S. Park, S. R. Park, S. W. Han, J. Y. Dong, J. S. Shin,
Adv. Synth. Catal. 2014, 356, 212–220.
19] A. Brugging, E. C. Roos, E. De Vroom, Org. Process
[
[
4] a) L. P. B. GonÅalves, O. A. C. Antunes, E. G. Oes-
treicher, Org. Process Res. Dev. 2006, 10, 673–677;
b) W. Hummel, M. Kuzu, B. Geueke, Org. Lett. 2003, 5,
Res. Dev. 1998, 2, 128–133.
[20] G. Matfin, R. E. Pratley, Ther. Adv. Endocrinol. Metab.
2010, 1, 5–14.
3
649–3650; c) T. Li, A. B. Kootstra, I. G. Fotheringham,
Org. Process Res. Dev. 2002, 6, 533–538; d) E. S. Park,
J. Y. Dong, J. S. Shin, Org. Biomol. Chem. 2013, 11,
[21] Relative reactivity was calculated by comparing the ini-
tial reaction rates measured at 20 mM (R)-a-MBA and
20 mM 2a or 2h.
[22] A. Iwasaki, K. Matsumoto, J. Hasegawa, Y. Yasohara,
Appl. Microbiol. Biotechnol. 2012, 93, 1563–1573.
[23] a) C. B’Hymer, M. Montes-Bayon, J. A. Caruso, J. Sep.
Sci. 2003, 26, 7–19; b) R. Bhushan, H. Brꢅckner,
Amino Acids 2004, 27, 231–247.
6
929–6933; e) J. Y. Hwang, J. Park, J. H. Seo, M. Cha,
B. K. Cho, J. Kim, B. G. Kim, Biotechnol. Bioeng. 2009,
02, 1323–1329.
1
[
5] a) M. A. Wegman, M. H. A. Janssen, F. van Rantwijk,
R. A. Sheldon, Adv. Synth. Catal. 2001, 343, 559–576;
b) J. M. Clemente-Jimꢃnez, S. Martꢄnez-Rodrꢄguez, F.
Adv. Synth. Catal. 2014, 356, 3505 – 3509
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