Kinetics and enantioselectivity of the Baeyer-Villiger oxidation of cyclohexanones by chiral tetrapyridyl oxoiron(IV) complex

被引:9
作者
Turcas, Ramona [1 ]
Lakk-Bogath, Dora [1 ]
Speier, Gabor [1 ]
Kaizer, Jozsef [1 ]
机构
[1] Univ Pannonia, Dept Chem, H-8200 Veszprem, Hungary
关键词
Biomimetics; Baeyer-Villiger oxidation; Iron(IV)-oxo complex; Enantioselectivity; Kinetics; HYDROGEN-PEROXIDE; MONOOXYGENASE; KETONES; CHEMISTRY; CELLS;
D O I
10.1016/j.inoche.2018.04.024
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The previously reported oxoiron(IV) complex, [Fe-IV(asN4Py)(O)](2+) with chiral pentadentate ligand, asN4Py (asN4Py = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine), is effective for the Baeyer-Villiger oxidation of cyclohexanone derivatives. The reaction is shown to be first order in both cyclohexanone and the oxoiron(IV) species. The second order rate constant is smaller by one order of magnitude than that obtained for the related achiral [Fe-IV(N4Py)(O)](2+) complex. Oxidation of 4-substituted cyclohexanone derivatives by the chiral oxoiron (IV) complex attains moderate enantioselectivities up to 45% enantiomeric excess (ee).
引用
收藏
页码:141 / 144
页数:4
相关论文
共 32 条
[1]  
Backvall J.-E., 2010, MODERN OXIDATION MET
[2]  
Baeyer A., 1899, BER DTSCH CHEM GES, V32, P3625, DOI DOI 10.1002/CBER.189903203151
[3]   Hot spots for the protein engineering of Baeyer-Villiger monooxygenases [J].
Balke, Kathleen ;
Beier, Andy ;
Bornscheuer, Uwe T. .
BIOTECHNOLOGY ADVANCES, 2018, 36 (01) :247-263
[4]  
Bolm C, 1997, ADV CAT PROCESS, V2, P43
[5]   Biotransformation of cyclohexanone using immobilized Geotrichum candidum NCYC49 -: Factors affecting the selectivity of the process [J].
Carballeira, JD ;
Alvarez, E ;
Sinisterra, JV .
JOURNAL OF MOLECULAR CATALYSIS B-ENZYMATIC, 2004, 28 (01) :25-32
[6]   Catalytic Asymmetric Baeyer-Villiger Oxidation in Water by Using PtII Catalysts and Hydrogen Peroxide: Supramolecular Control of Enantioselectivity [J].
Cavarzan, Alessandra ;
Bianchini, Giulio ;
Sgarbossa, Paolo ;
Lefort, Laurent ;
Gladiali, Serafino ;
Scarso, Alessandro ;
Strukul, Giorgio .
CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (32) :7930-7939
[7]   PURIFICATION AND PROPERTIES OF CYCLOHEXANONE OXYGENASE FROM NOCARDIA-GLOBERULA CL1 AND ACINETOBACTER NCIB-9871 [J].
DONOGHUE, NA ;
NORRIS, DB ;
TRUDGILL, PW .
EUROPEAN JOURNAL OF BIOCHEMISTRY, 1976, 63 (01) :175-192
[8]   Regio- and stereoselective synthesis of chiral nitrilolactones using Baeyer-Villiger monooxygenases [J].
Fink, Michael J. ;
Snajdrova, Radka ;
Winninger, Alexander ;
Mihovilovic, Marko D. .
TETRAHEDRON, 2016, 72 (46) :7241-7248
[9]  
FISCHER RT, 1991, J BIOL CHEM, V266, P6124
[10]   Identification of a Baeyer-Villiger monooxygenase sequence motif [J].
Fraaije, MW ;
Kamerbeek, NM ;
van Berkel, WJH ;
Janssen, DB .
FEBS LETTERS, 2002, 518 (1-3) :43-47