Exploring the Hydroxylation−Dehydrogenation Connection: Novel Catalytic Activity of Castor Stearoyl-ACP Δ9 Desaturase
- 6 March 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (13) , 3277-3283
- https://doi.org/10.1021/ja012252l
Abstract
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 enantioselectivitya 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.Keywords
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