Catalysis Science & Technology
Paper
minimised before the modification of the inhibitor. The acyl Acknowledgements
donor (DVA) and acyl acceptor (1-octanol) were sequentially
The study has been funded by Formas, grant No. 211-2013-70
and European Union's Seventh Framework Program for re-
search, technological development and demonstration under
grant No. 289253. EnginZyme (Sweden) are acknowledged for
the EziG3 carriers. Professor emeritus Karl Hult is acknowl-
edged for valuable discussions and general input.
built on S11 to resemble a tetrahedral intermediate during
deacylation. Energy minimisations and MD runs (0.005 ns)
were made for each added carbon. After the tetrahedral inter-
mediate was built MD runs for 0.02 ns followed by energy
minimisations was done for each structure.
Analytic methods
References
GC-analysis. Gas chromatography (GC) analysis was
performed on a Hewlett Packard HP 5890 series II gas chro-
matograph with an Agilent J&W CP-Sil 5 CB column (30 m ×
0.25 mm) and a flame ionization detector (FID). GC program
according to: inlet temperature of 275 °C, detector 300 °C,
initial 60 °C, and final 320 °C (20 °C min−1) with a 2 min
hold. The relative response factors (RRFs) were calculated
according to Scanlon et al.26 Toluene, deuterated toluene (tol-
uene-d8), chloroform, or deuterated chloroform (chloroform-
d) were used as solvent. Retention times: butane diol vinyl
ether (BVE) 3.6 min, 1-octanol 4.3 min, dimethyl succinate
3.9 min, dimethyl adipate 5.4 min, divinyl adipate (DVA) 6.1
min, diphenyl ether 6.6 min, dimethyl suberate 6.7 min, di-
methyl sebacate 8.0 min, octyl vinyl adipate (OVA) 9.6 min,
octyl methyl succinate 8.3 min, 4-(vinyloxy)butyl vinyl adipate
(BVEVA) 9.0 min, octyl methyl adipate 9.3 min, octyl methyl
suberate 10.3 min, octyl methyl sebacate 11.2 min, bisBVEA
11.4 min, dioctyl succinate 11.4 min, dioctyl adipate 12.2
min, dioctyl suberate 13.0 min, dioctyl sebacate 13.7 min.
NMR analysis. 1H-Nuclear magnetic resonance (NMR)
spectroscopy was performed on a Bruker AM 400 NMR
spectrometer. Spectra were generated with 16 scans. Toluene-
d8 or chloroform-d (0.05% v/v TMS, for calibration of the
NMR spectra) was used as solvent.
1 I. Bassanini, K. Hult and S. Riva, Beilstein J. Org. Chem.,
2015, 11, 1583–1595.
2 C.-H. Wong and S. C. Zimmerman, Chem. Commun.,
2013, 49, 1679–1695.
3 S.-Y. Baek, Y.-W. Kim, K. Chung, S.-H. Yoo, N. K. Kim and
Y.-J. Kim, Ind. Eng. Chem. Res., 2012, 51, 3564–3568.
4 H. Bart, J. Reidetschläger, K. Schatka and A. Lehmann, Int. J.
Chem. Kinet., 1994, 26, 1013–1021.
5 A. Sharma, S. Chattopadhyay and V. R. Mamdapur,
Biotechnol. Lett., 1995, 17, 939–942.
6 R. Shelkov, M. Nahmany and A. Melman, J. Org. Chem.,
2002, 67, 8975–8982.
7 H. Ogawa, T. Chihara and K. Taya, J. Am. Chem. Soc.,
1985, 107, 1365–1369.
8 V. Santacroce, F. Bigi, A. Casnati, R. Maggi, L. Storaro, E.
Moretti, L. Vaccaro and G. Maestri, Green Chem., 2016, 18,
5764–5768.
9 M. Lobell and M. P. Schneider, J. Chem. Soc., Perkin Trans. 1,
1993, 1713–1714.
10 A. Mautner, B. Steinbauer, S. Orman, G. Russmüller, K.
Macfelda, T. Koch, J. Stampfl and R. Liska, J. Polym. Sci.,
Part A: Polym. Chem., 2016, 54, 1987–1997.
11 I. Mathews, M. Soltis, M. Saldajeno, G. Ganshaw, R. Sala, W.
Weyler, M. A. Cervin, G. Whited and R. Bott, Biochemistry,
2007, 46, 8969–8979.
Conclusions
12 L. Wiermans, S. Hofzumahaus, C. Schotten, L. Weigand, M.
Schallmey, A. Schallmey and P. Domínguez de María,
ChemCatChem, 2013, 5, 3719–3724.
13 K. Szymańska, K. Odrozek, A. Zniszczoł, G. Torrelo, V. Resch,
U. Hanefeld and A. B. Jarzębski, Catal. Sci. Technol., 2016, 6,
4882–4888.
14 N. de Leeuw, G. Torrelo, C. Bisterfeld, V. Resch, L. Mestrom,
E. Straulino, L. van der Weel and U. Hanefeld, Adv. Synth.
Catal., 2018, 360, 242–249.
15 H. Land, P. Hendil-Forssell, M. Martinelle and P. Berglund,
Catal. Sci. Technol., 2016, 6, 2897–2900.
16 M. L. Contente, A. Pinto, F. Molinari and F. Paradisi, Adv.
Synth. Catal., 2018, 360, 4814–4819.
17 L. Mestrom, J. G. Claessen and U. Hanefeld, ChemCatChem,
2019, 11, 2004–2010.
18 I. C. Perdomo, S. Gianolio, A. Pinto, D. Romano, M. L.
Contente, F. Paradisi and F. Molinari, J. Agric. Food Chem.,
2019, 67, 6517–6522.
19 P. Hendil-Forssell, Rational engineering of esterases for
improved amidase specificity in amide synthesis and
A novel synthesis route for mono-substitution of symmetric
diesters utilising the single point mutant MsAcT L12A as cat-
alyst was developed. The combined results show that the
immobilized MsAcT variants yields catalyst for different ap-
plications. MsAcT L12A is a selective catalyst capable of
reacting one group out of two identical chemical groups. In
contrast, the double point mutant MsAcT T93A/F154A poses
as a more versatile catalyst. It can accommodate dicarboxylic
esters of varying lengths and is able to catalyse di-substituted
adipate. Furthermore, immobilising the MsAcT enabled the
catalyst to work under solvent-free conditions and therefore
it could be recycled. As MsAcT accepts amines as acyl accep-
tor interesting amide derivatives might extend the synthetic
scope.
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 2019
Catal. Sci. Technol.