Insights into the mechanism of fatty acid photodecarboxylase: A theoretical investigation

[Display omitted] •Bimolecular mechanism of FAP is energetically preferred.•The FADH-based intermediates are in better conformity with the high quantum yield.•The UV spectrum of intermediate FADH• correlates well with experimentally spectrum. Fatty acid photodecarboxylase (FAP), was reported recentl...

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Bibliographic Details
Published in:Chemical physics letters 2021-05, Vol.771, p.138550, Article 138550
Main Authors: Hong, Pan, Ning, Li-Chao, Wu, An-An, Tan, Kai, Lu, Xin
Format: Article
Language:English
Subjects:
DFT
Fatty acid photodecarboxylase
Lumiflavin and FAD
Photodecarboxylation
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Summary:[Display omitted] •Bimolecular mechanism of FAP is energetically preferred.•The FADH-based intermediates are in better conformity with the high quantum yield.•The UV spectrum of intermediate FADH• correlates well with experimentally spectrum. Fatty acid photodecarboxylase (FAP), was reported recently that can catalyze fatty acid decarboxylation to afford n-alkanes in blue light. A trimolecular photocycle mechanism involving an unidentified proton donor HX was proposed, which is seemingly incompatible with the observed high quantum yield (>80%). Herein, we present an energetic preferred bimolecular mechanism by DFT that involves FADH-based intermediates. Our present work suggests that the light-capturing organic molecule itself, lumiflavin (FI) of FAD, may act as a metal-free photocatalyst for the photodecarboxylation of fatty acids to afford hydrocarbons in organic synthesis.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2021.138550