A DFT study on the chiral synthesis of R-phenylacetyl carbinol within the quantum chemical cluster approach

被引:5
作者
Alvarado, Omar [1 ]
Lizana, Ignacio [1 ]
Jana, Gonzalo [2 ]
Tunon, Inaki [3 ]
Delgado, Eduardo [1 ]
机构
[1] Univ Concepcion, Dept Fis Quim, Fac Ciencias Quim, Concepcion, Chile
[2] Univ Andres Bello, Fac Ciencias Exactas, Sede Concepcion, Dept Ciencias Quim, Santiago, Chile
[3] Univ Valencia, Dept Quim Fis, E-46100 Burjassot, Spain
关键词
ALPHA-HYDROXY KETONES; ACETOHYDROXYACID SYNTHASE; CARBOLIGATION REACTION; ESCHERICHIA-COLI; ENZYME; INTERMEDIATE; SUBSTRATE; CATALYSIS;
D O I
10.1016/j.cplett.2017.03.066
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The reaction pathway leading to R-phenylacetyl carbinol within the quantum chemical cluster approach is addressed by means of density functional theory (DFT) calculations. The study includes calculation of Fukui functions, activation free energies, and potential energy surface scans, both in gas and solution phase. The protonation states of the nitrogen atoms of the pyrimidine moiety are determined. The reaction appears to be slightly exergonic (Delta G(0) = -5.6 and -4.0 kcal/mol for gas and solution phase, respectively) following a concerted synchronous mechanism having activation free energy barriers of 16.2 and 13.3 kcal/mol, in gas phase and solution phase, respectively. (C) 2017 Published by Elsevier B.V.
引用
收藏
页码:30 / 34
页数:5
相关论文
共 17 条
[1]   Thiamine pyrophosphate dependent enzyme catalyzed reactions: Stereoselective C-Cbond formations in water [J].
Demir, Ayhan S. ;
Ayhan, Peruze ;
Sopaci, S. Betuel .
CLEAN-SOIL AIR WATER, 2007, 35 (05) :406-412
[2]  
Duggleby RG, 2000, J BIOCHEM MOL BIOL, V33, P1
[3]   Column flow reactor using acetohydroxyacid synthase I from Escherichia coli as catalyst in continuous synthesis of R-phenylacetyl carbinol [J].
Engel, S ;
Vyazmensk, M ;
Berkovich, D ;
Barak, Z ;
Merchuk, J ;
Chipman, DM .
BIOTECHNOLOGY AND BIOENGINEERING, 2005, 89 (06) :733-740
[4]   Substrate range of acetohydroxy acid synthase I from Escherichia coli in the stereoselective synthesis of α-hydroxy ketones [J].
Engel, S ;
Vyazmensky, M ;
Berkovich, D ;
Barak, Z ;
Chipman, DM .
BIOTECHNOLOGY AND BIOENGINEERING, 2004, 88 (07) :825-831
[5]   Role of a conserved arginine in the mechanism of acetohydroxyacid synthase - Catalysis of condensation with a specific ketoacid substrate [J].
Engel, S ;
Vyazmensky, M ;
Vinogradov, M ;
Berkovich, D ;
Bar-Ilan, A ;
Qimron, U ;
Rosiansky, Y ;
Barak, Z ;
Chipman, DM .
JOURNAL OF BIOLOGICAL CHEMISTRY, 2004, 279 (23) :24803-24812
[6]   Acetohydroxyacid synthase:: A new enzyme for chiral synthesis of R-phenylacetylcarbinol [J].
Engel, S ;
Vyazmensky, M ;
Geresh, S ;
Barak, Z ;
Chipman, DM .
BIOTECHNOLOGY AND BIOENGINEERING, 2003, 83 (07) :833-840
[7]   Biocatalytic Strategies for the Asymmetric Synthesis of α-Hydroxy Ketones [J].
Hoyos, Pilar ;
Sinisterra, Josep-Vicent ;
Molinari, Francesco ;
Alcantara, Andres R. ;
De Maria, Pablo Dominguez .
ACCOUNTS OF CHEMICAL RESEARCH, 2010, 43 (02) :288-299
[8]   Computational study on the carboligation reaction of acetohidroxyacid synthase: New approach on the role of the HEThDP- intermediate [J].
Jana, Gonzalo ;
Jimenez, Veronica ;
Villa-Freixa, Jordi ;
Prat-Resina, Xavier ;
Delgado, Eduardo ;
Alderete, Joel .
PROTEINS-STRUCTURE FUNCTION AND BIOINFORMATICS, 2010, 78 (07) :1774-1788
[9]   Thiamin diphosphate in biological chemistry: exploitation of diverse thiamin diphosphate-dependent enzymes for asymmetric chemoenzymatic synthesis [J].
Mueller, Michael ;
Gocke, Doerte ;
Pohl, Martina .
FEBS JOURNAL, 2009, 276 (11) :2894-2904
[10]   Crystal structure of yeast acetohydroxyacid synthase: A target for herbicidal inhibitors [J].
Pang, SS ;
Duggleby, RG ;
Guddat, LW .
JOURNAL OF MOLECULAR BIOLOGY, 2002, 317 (02) :249-262