FUNCTIONAL-GROUP DIVERSITY IN ENZYMATIC OXYGENATION REACTIONS CATALYZED BY BACTERIAL FLAVIN-CONTAINING CYCLOHEXANONE OXYGENASE

被引:119
作者
BRANCHAUD, BP
WALSH, CT
机构
[1] MIT, DEPT CHEM, CAMBRIDGE, MA 02139 USA
[2] MIT, DEPT BIOL, CAMBRIDGE, MA 02139 USA
关键词
D O I
10.1021/ja00293a054
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The bacterial (Acinetobacter) flavoprotein monooxygenase cyclohexanone oxygenase was found by spectrophotometric NADPH consumption assays and product analysis studies to perform oxygenation reaction on ketones, aldehydes, sulfides,selenides, boronic acids, a phosphite ester, and an iodide ion, Kinetic parameters (Km Vmax) are reported for these substrates. The relevance of these results to possible active oxygen-transfer species in this enzyme is discussed. The potential utility of boronic acids as general probes for nucleophilic oxygen-transfer capability in oxygenases and in model chemistry is analyzed. The potential utility of cyclohexanone oxygenase as an enatioselective and/or chemoselective oxidant for organic molecules is assessed. Unsuccessful attempts at exploiting the 2,3-signatropic rearrangement of allyl sulfoxides and allyl selenoxides for mechanism-based inactivation of cyclohexanone oxygenase are reported. The use of the facile 2,3-sigmatropic rearrangement of allyl selenoxides to generate electrophilic allyl selenates for the design of mechanism-based inactivators for other enzymes is proposed.
引用
收藏
页码:2153 / 2161
页数:9
相关论文
共 85 条
[1]  
Ballou D.P., 1982, Flavins andflavoproteins, P301
[2]  
BARMAN TE, 1969, ENZYME HDB, V1, P23
[3]  
BARTON D, 1979, COMPREHENSIVE ORGANI, V1, P920
[4]  
BEATY NB, 1981, J BIOL CHEM, V256, P4619
[5]  
BEATY NB, 1981, J BIOL CHEM, V256, P4611
[6]   THERMAL RACEMIZATION OF ALLYLIC SULFOXIDES AND INTERCONVERSION OF ALLYLIC SULFOXIDES AND SULFENATES - MECHANISM AND STEREOCHEMISTRY [J].
BICKART, P ;
CARSON, FW ;
JACOBUS, J ;
MILLER, EG ;
MISLOW, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (18) :4869-&
[7]   HEXAMETHYLPHOSPHORAMIDE-MEDIATED CONJUGATE ADDITION OF (ALKYLTHIO)ALLYLLITHIUM (PHENYLTHIO)ALLYLLITHIUM AND (PHENYLSELENO)ALLYLLITHIUM REAGENTS TO 2-CYCLOPENTENONE [J].
BINNS, MR ;
HAYNES, RK .
JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (19) :3790-3795
[8]  
BOYER PD, 1963, ENZYMES, V7, P40
[9]   MONOOXYGEN DONATION POTENTIAL OF 4A-HYDROPEROXYFLAVINS AS COMPARED WITH THOSE OF A PERCARBOXYLIC ACID AND OTHER HYDROPEROXIDES - MONOOXYGEN DONATION TO OLEFIN, TERTIARY AMINE, ALKYL SULFIDE, AND IODIDE-ION [J].
BRUICE, TC ;
NOAR, JB ;
BALL, SS ;
VENKATARAM, UV .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (08) :2452-2463
[10]  
BRUICE TC, 1980, BIOMIMETIC CHEM, P88