Combined photoredox/engineered P450 enzymatic direct dioxygen-functionalization of arylalkanes to chiral acyloins

Abstract

To date, the examples of difunctionalization of alkanes to directly incorporate two functional groups are very limited. In this study, we combined photo-organo redox catalysis and P450 biocatalysts to obtain...

Regioselective and enantioselective propargylic hydroxylations catalyzed by P450tol monooxygenases

“…In our previous work, we have obtained several cytochrome P450 monooxygenases (P450DA, P450PL2-2) (Cui et al 2023 , 2019 ; Deng et al 2022 ; Wan et al 2022 ; Wang et al 2022 ; Xie et al 2020 , 2023 ) and also constructed five recombinant Escherichia coli strains (P450tol-1 to P450tol-5) harboring P450tol monooxygenase from Rhodococcus coprophilus TC-2 (Chen et al 2022 ; Li et al 2014 ) and five pairs of redox partner Fdx-FdR (ferredoxin-ferredoxin reductase) from P. lavamentivorans DS-1 (Wu et al 2018 ). With these P450s in hand, but-1-yn-1-ylbenzene ( 1a ) was used as a model substrate to explore the hydroxylation activity and stereoselectivity of these recombinant P450 strains.…”

“…However, P450s as an effective and versatile catalyst for the enantioselective hydroxylation of propargylic C-H bonds has not been available in literature. In light of our ongoing interests in P450s-catalyzed asymmetric hydroxylation reactions with a broad substrate range and widely applications (Cui et al 2023 , 2019 ; Deng et al 2022 ; Wan et al 2022 ; Wang et al 2022 ; Xie et al 2020 , 2023 ), we herein describe chiral propargylic alcohols were synthesized from the simple alkynes by P450tol catalyzed asymmetric propargylic C-H bonds hydroxylation with regio- and stereoselectivity (Fig. 1 b).…”

Asymmetric Synthesis of β-Hydroxyphosphonates via a Chemoenzymatic Cascade

“…However, the conversion of β-ketophosphonate into unidentified compounds resulted in a significant decrease in yields compared to the reaction without pyridinium chlorochromate. Fortunately, the use of photooxidation has been found to have advantages in generating carbonyl or hydroxyl functionalities (Figure C). − We then tried to employ a photo-oxidative reaction following the chemical reaction to synthesize β-ketophosphonates in this work. The photo-oxidative approach successfully resulted in decreasing ratios of racemic β-hydroxyphosphonates and increasing yields of β-ketophosphonates in the chemical step, ultimately achieving yields of up to 98%.…”