2022
DOI: 10.3389/fchem.2022.950149
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Enzyme-catalyzed allylic oxidation reactions: A mini-review

Abstract: Chiral allylic oxidized products play an increasingly important role in the pharmaceutical, agrochemical, and pharmaceutical industries. Biocatalytic C–H oxyfunctionalization to synthesize allylic oxidized products has attracted great attention in recent years, with the ability to simplify synthetic approaches toward complex compounds. As a result, scientists have found some new enzymes and mutants through techniques of gene mining and enzyme-directed evolution in recent years. This review summarizes the recen… Show more

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Cited by 9 publications
(9 citation statements)
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“…Nonetheless, significant challenges remain in the asymmetric epoxidation of unfunctionalized alkenes. Compounds containing C=C double bonds usually undergo hydroxylation of allyl groups or epoxidation of C=C double bonds [106] . The mechanism of which reaction the enzyme prefers is currently unknown, but the specific location of a given substrate in the binding pocket is crucial to its oxidative “fate’’.…”
Section: Discussionmentioning
confidence: 99%
“…Nonetheless, significant challenges remain in the asymmetric epoxidation of unfunctionalized alkenes. Compounds containing C=C double bonds usually undergo hydroxylation of allyl groups or epoxidation of C=C double bonds [106] . The mechanism of which reaction the enzyme prefers is currently unknown, but the specific location of a given substrate in the binding pocket is crucial to its oxidative “fate’’.…”
Section: Discussionmentioning
confidence: 99%
“…11,12 Enzymatic strategies are underdeveloped; 13 examples on few selected substrates include the use of cytochrome P450s and unspecific peroxygenases (UPOs). 14,15 UPOs are well known to selectively catalyze the oxyfunctionalization of ethylbenzene at the benzylic position to the corresponding enantiopure (R)-1-phenylethanol, and can also further oxidize both enantiomers of 1phenylethanol to acetophenone, 16 yet remain to be further explored with substituted cyclohexene substrates, in particular with regard to stereoselectivity. 14,17 Thus, we report an alternative enzymatic synthesis (Scheme 1C) of (1S,3R)-3-hydroxycyclohexanecarbonitrile 5 starting from the commercially available pro-chiral cyclohexene-1nitrile 1.…”
Section: ■ Introductionmentioning
confidence: 99%
“…Intermediate 3 not being commercially available, a C–H oxyfunctionalization step is required to introduce the ketone functional group into the commercially available pro-chiral starting material 1 . Regioselective allylic oxidation of alkenes, in particular substituted cyclohexenes, remains challenging and reported chemical strategies include the use of hypervalent iodide reagents, transition metal catalysis, , or photocatalysis. , Enzymatic strategies are underdeveloped; examples on few selected substrates include the use of cytochrome P450s and unspecific peroxygenases (UPOs). , UPOs are well known to selectively catalyze the oxyfunctionalization of ethylbenzene at the benzylic position to the corresponding enantiopure ( R )-1-phenylethanol, and can also further oxidize both enantiomers of 1-phenylethanol to acetophenone, yet remain to be further explored with substituted cyclohexene substrates, in particular with regard to stereoselectivity. , …”
Section: Introductionmentioning
confidence: 99%
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“…In comparison to alb G– alb P1, which produces 1 – 3 , expression of albG – albP1 without albU only produced 1 , supporting the intermediacy of 2 and that AlbP1 acts only on 2 (Figure ). Allylic oxidation at C-6 of 2 by AlbP1 appears to be a likely pathway to 3 , although this would require at least one additional step to form the C-6 ketone and account for the concomitant change of the C-7(19) alkene in 2 into a methyl at C-19. One hypothesis is that AlbU can isomerize the allylic alcohol into an enol, which would tautomerize to the ketone (Figure S46A).…”
mentioning
confidence: 99%