Exploring the hydroxylation-dehydrogenation connection:: Novel catalytic activity of castor stearoyl-ACP Δ9 desaturase

被引：49

作者：

Behrouzian, B

Savile, CK

Dawson, B

Buist, PH ^{[1
]}

Shanklin, J

机构：

[1] Brookhaven Natl Lab, Dept Biol, Upton, NY 11973 USA

[2] Carleton Univ, Ottawa Carleton Chem Inst, Dept Chem, Ottawa, ON K1S 5B6, Canada

[3] Hlth Canada, Hlth Prod & Food Branch, Div Res Serv, Ottawa, ON K1A 0L2, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 13期

关键词：

D O I：

10.1021/ja012252l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The novel product profile obtained by incubating chiral fluorinated substrate analogues with castor stearoyl-ACP Delta(9) desaturase has been rationalized through a series of labeling studies. It was found that the introduction of the Z-double bond between C-9 and C-10 of the parent substrate occurs with pro-R enantioselectivity-a result that accounts for the observed stereochemistry of oxidation products derived from (9R)- and (9S)-9-fluorostearoyl-ACP. Oxidation of (9R)-9-fluorostearoyl-ACP occurs via at least two rapidly interchanging substrate conformations in the active site as detected by reaction pathway branching induced by deuteration at C-10 and C-11. Hydroxylation and desaturation of this substrate share the same site of initial oxidative attack.

引用

页码：3277 / 3283

页数：7

共 42 条

[1] CYTOCHROME P450-CATALYZED HYDROXYLATION OF HYDROCARBONS - KINETIC DEUTERIUM-ISOTOPE EFFECTS FOR THE HYDROXYLATION OF AN ULTRAFAST RADICAL CLOCK [J].