Journal of the American Chemical Society p. 7928 - 7935 (1984)
Update date:2022-08-11
Topics:
Katopodis, Andreas, G.
Wimalasena, Kandatege
Lee, Joseph
May, Sheldon W.
In previous work we have established that the "ω-hydroxylation" system of P. oleovorans readily converts terminal olefins to the corresponding 1,2-oxides and does so stereoselectively.We also demonstrated loss of olefin configuration during enzymatic epoxidation, a result inconsistent with a concerted epoxidation mechanism (J.Am.Chem.Soc. 1977, 99, 2017-2024).Since loss of olefin configuration is unprecedented for monooxygenase-catalyzed epoxidations these studies have been confirmed with isolated enzymes and further extended in order to probe the mechanism of non-heme iron monooxygenase catalysis.Enzymatic epoxidation of both cis- and trans-1-deuterio-1-octene proceeds with about 70percent inversion of the olefinic configuration, with corresponding results being obtained for the two olefins.As we reported in a preliminary communication (Bio/Technology 1983, 1, 677-686, the ω-hydroxylation system also produces aldehydes from olefins.Aldehyde formations exhibits the reaction characteristics expected for the usual oxygenase pathway.Deuterium migration from C-1 to C-2 occurs in formation of aldehyde from olefin, although loss of deuterium also occurs.The ω-hydroxylation system was found to efficiently catalyze O-demethylation of heptyl methyl ether, the first demonstration of such activity for a non-heme iron monooxygenase of this type.Taken together, the results provide support for a two-step mechanism involving enzyme generated species with cationic and/or radical character, which accounts for the stereoselectivity, configurational loss, substrate specificity, formation of aldehydes with deuterium migration, and demethylation activity exhibited by this enzyme system.
View MoreShijiazhuang Yunxuan Im&Export Co.,Ltd.
Contact:+86-311-83037514
Address:No.6 Hongbin Road
Contact:13120882795;+86-21-34621078;+86-021-31122318
Address:Suite 2,No.2715 Longwu Road
website:http://www.josunpharma.com
Contact:+86-311-80715268 80766839
Address:No.39, Zhaiying Street, Shijaizhuang,Hebei,China
Chongqing Changfeng Chemical Co., Ltd.
website:http://www.changfengchem.com
Contact:+86-23-67896333
Address:30th Floor, Longhu Ziduxingzuo Building A, 1st Branch,YuSong Rd., Yubei District, Chongqing, China
Binzhou Holly Pharmaceutical Co.,Ltd.
Contact:74517
Address:No.15 Dapu Road,Huangpu District Shanghai,P.R.China
Doi:10.1002/chem.201503000
(2015)Doi:10.1039/c0gc00523a
(2011)Doi:10.1139/v58-248
(1958)Doi:10.1021/acs.jmedchem.7b00637
(2017)Doi:10.1023/A:1013707808047
(2001)Doi:10.1016/0022-328X(95)05748-E
(1996)