Exploring the Hydroxylation−Dehydrogenation Connection:  Novel Catalytic Activity of Castor Stearoyl-ACP Δ9 Desaturase

Exploring the Hydroxylation−Dehydrogenation Connection:  Novel Catalytic Activity of Castor Stearoyl-ACP Δ9 Desaturase

The novel product profile obtained by incubating chiral fluorinated substrate analogues with castor stearoyl-ACP Δ9 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...

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Veröffentlicht in:Journal of the American Chemical Society 2002-04, Vol.124 (13), p.3277-3283
Hauptverfasser: Behrouzian, Behnaz, Savile, Christopher K, Dawson, Brian, Buist, Peter H, Shanklin, John
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Sprache:eng
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Analytical, structural and metabolic biochemistry
Biological and medical sciences
Enzymes and enzyme inhibitors
Fundamental and applied biological sciences. Psychology
General aspects, investigation methods
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container_issue 13
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container_title Journal of the American Chemical Society
container_volume 124
creator Behrouzian, Behnaz
Savile, Christopher K
Dawson, Brian
Buist, Peter H
Shanklin, John
description The novel product profile obtained by incubating chiral fluorinated substrate analogues with castor stearoyl-ACP Δ9 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.
doi_str_mv 10.1021/ja012252l
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subjects Analytical, structural and metabolic biochemistry
Biological and medical sciences
Enzymes and enzyme inhibitors
Fundamental and applied biological sciences. Psychology
General aspects, investigation methods
title Exploring the Hydroxylation−Dehydrogenation Connection:  Novel Catalytic Activity of Castor Stearoyl-ACP Δ9 Desaturase
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