Bio‐based α,ω‐Functionalized Hydrocarbons from Multi‐step Reaction Sequences with Bio‐ and Metallo‐catalysts Based on the Fatty Acid Decarboxylase OleT_JE

Abstract

OleT from Jeotgalicoccus sp. ATCC 8456 catalyzes the decarboxylation of ω‐functionalized fatty acids to the corresponding alkenols, which can themselves serve as starting material for the synthesis of polymers and fine chemicals. To show the versatility of possible reactions, a series of in vitro reaction cascades was developed where an alkenol produced by the decarboxylation of ω‐hydroxy fatty acids can be further converted into alkenylamines and diols. By coupling OleT with an alcohol dehydrogenase or alcohol oxidase as well as an amino‐transaminase, an oxidative decarboxylation followed by the oxidation of the terminal alcohol and a subsequent reductive transamination could be carried out. By using different cofactors or electron sources, the reactions could be performed sequentially or simultaneously. The combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo‐enzymatic cascade provides a novel way to synthesize long‐chain diols.

Nonconventional regeneration of redox enzymes – a practical approach for organic synthesis?

“…105 In addition, some naturally occurring P450 monooxygenases also exhibit some peroxygenase activity. [106][107][108][109][110][111][112][113] Peroxygenases are heme-enzymes naturally utilising the H 2 O 2 shunt pathway to form the catalytically active compound I (vide infra). Cong and coworkers hypothesised that P450 monooxygenases lack a catalytic base in the enzyme active site to mediate the deprotonation of the initial H 2 O 2 adduct to the Fe III resting state (Fig.…”

One-Pot Combination of Metal- and Bio-Catalysis in Water for the Synthesis of Chiral Molecules

“…Thus, these drawbacks could be addressed with the following settings: (i) chemoenzymatic reaction was performed in a sequential fashion (one-pot/two-step methodology) in an organic solvent (MTBE, methyl tert-butyl ether); (ii) encapsulation of the decarboxylase in a PVA/PEG cryogel (bsPAD@PVA/PEG) [88]; and (iii) an extra intermediate drying step (employing anhydrous MgSO4) before the metathesis reaction (Scheme 16C). Finally, this combination of reactions has been very recently extended by the same authors to ω-hydroxy fatty acids [80].…”

“…Several types of metathesis transformations (RCM (ring-closing metathesis) and CM (cross-metathesis), among others) have been carried out in water by: (i) introducing modifications in the catalyst structure; (ii) using co-solvents; or (iii) employing surfactants [73][74][75]. Thus, in this section, we cover the fruitful combination of two different Ru-catalyzed metathesis protocols (RCM and CM) in aqueous media with several biocatalyzed organic reactions [76][77][78][79][80]. Although none of the discussed protocols permits the synthesis of enantiopure products, they constitute very important contributions in the field of chemoenzymatic cascade processes performed in aqueous media and are worth mention in this review.…”

“…Not only the Ru-catalyzed ring-closing metathesis (RCM) of different diallyl compounds, but also the Ru-catalyzed cross-metathesis (CM) of functionalized olefins has been productively assembled with different biotransformations [78][79][80]. Thus, the first work in this field was reported by Zhao, Hartwig and co-workers in 2014 by describing the combination of the ruthenium-catalyzed CM between 10-undecenoic acid and trans-3-hexene with the subsequent epoxidation of the in situ-generated 10-tridecenoic acid using P450 BM3 from Bacillus megaterium in a biphasic medium [78].…”

Chemo-enzymatic cascades to produce cycloalkenes from bio-based resources

“…Furthermore, enzymes may be combined with organometallic catalysts to assemble chemoenzymatic cascades to perform useful one-pot transformations unattainable with enzymes or small-molecule catalysts alone [8][9][10][11][12][13] . In the past 6 years, significant progress have been made in combining enzymes with organometallic catalysts [14][15][16][17][18][19][20][21] , including photocatalysts [22][23][24] . For this purpose, different strategies were implemented to accommodate the incompatible reactivities in a single vessel.…”