Phenyl Sulfide Research Articles

Enantioselectivity in Vanadium-Dependent Haloperoxidases of Different Marine Sources for Sulfide Oxidation to Sulfoxides.

This study explores the reasons behind the variations in the enantioselectivity of the sulfoxidation of methyl phenyl sulfide by marine-derived vanadium-dependent haloperoxidases (VHPOs). Twelve new VHPOs of marine organisms were overexpressed, purified, and tested for their ability to oxidize sulfide. Most of these marine enzymes exhibited nonenantioselective behavior, underscoring the uniqueness of AnVBPO from the brown seaweed Ascophyllum nodosum and CpVBPO from the red seaweed Corallina pilulifera, which produce (R)- and (S)-sulfoxides, respectively. The enantioselective sulfoxidation pathway is likely due to direct oxygen transfer within the VHPO active site. This was demonstrated through molecular docking and molecular dynamics simulations, which revealed differences in the positioning of sulfide within AnVBPO and CpVBPO, thus explaining their distinct enantioselectivities. Nonenantioselective VHPOs probably follow a different oxidation pathway, initiating with sulfide oxidation to form a positively charged radical. Further insights were gained from studying the catalytic effect of VO43- on H2O2-driven sulfoxidation. This research improves the understanding of VHPO-mediated sulfoxidation and aids in developing biocatalysts for sulfoxide synthesis.

Radical Cascade Cyclization of N-(o-Cyanobiaryl)acrylamides with Sulfonium Salts via Synergetic Photoredox and Copper Catalysis.

As the magic methyl effect is well acknowledged in pharmaceutical molecules, the development of simple and efficient methods for the installment of methyl groups on complex molecules is highly coveted. Hence, we provide a general strategy for radical cascade cyclization of N-(o-cyanobiaryl)acrylamides by utilizing sulfonium salts as the sources of methyl radical and merging photoredox and copper catalysis. This novel protocol can access a wide variety of methylation or remote thioether-substituted benzo-fused N-heterocycle derivatives, which can be easily transformed into diverse highly valuable sulfone and sulfoximine compounds via late-stage diversification. Moreover, to further demonstrate the synthetic utility of this conversion, the methyl(phenyl)sulfide, which serves as both raw material and byproduct, can be recovered and reused in this transformation. The scale-up experiment for the one-pot two-step process directly offers the target product in good yield under the standard conditions.

Keggin-type polyoxometalates/Amberlite nanocomposites as efficient catalysts for the aqueous oxidation of sulfides: Crucial roles of mono-iron and mono-manganese substituents

The condensation of Keggin-type polyoxometalates including H3PW12O40, H3PMo12O40, and their Mn(III) and Fe(III) derivatives with nano-structured Amberlite, nanoAmbN(Me)3Cl led to the formation of electrostatically immobilized polyoxometalates on the anion exchange polymer with a size less than ca. 70 nm. The nanocomposites were characterized by FT-IR, XRD, solid state diffuse-reflectance and solution UV–vis spectroscopy, TGA, BET and FESEM-EDX-Mapping and used for the oxidation of sulfides with periodate under aqueous and non-aqueous conditions. In spite of the small difference between the catalytic activity of H3PMo12O40 and H3PW12O40, the corresponding mono-iron and manganese substituted derivatives showed significantly different catalytic activities. Furthermore, nanoAmbN(Me)3@PW11MnO39 showed a high selectivity towards sulfone (72 %), compared to the highly chemoselective formation of sulfoxide in the presence of nanoAmbN(Me)3@PW11FeO39. NanoAmbN(Me)3@PW11FeO39 as the best catalyst of the series was recovered and reused at least six times for the oxidation of methyl phenyl sulfide. The increased catalytic activity of the iron-containing polyoxometalates than that of the corresponding manganese compounds was attributed to the Jahn-Teller distortion around the manganese(III) center.

Synthesis of flower-like covalent organic frameworks for photocatalytic selective oxidation of sulfide

BackgroundCovalent organic frameworks (COFs)-based photocatalysts have garnered significant attention for their potential in highly efficient and selective sulfide oxidation. However, the current synthesis methods of COF-based catalysts involve complex multi-step procedures, and better methods need to be upgraded for synthesis. MethodsIn this study, a flower-like COF-based photocatalyst (f-COFs) was synthesized by one-pot method at room temperature using zinc chloride (ZnCl2) as catalyst. The photocatalytic performance of f-COFs was investigated using methyl phenyl sulfide as substrate. Significant FindingsZinc ions remain on the f-COFs synthesized by this method. EDX analysis and XPS techniques were used to confirm the presence of zinc ions. The presence of zinc ions controls the self-assembly of COFs to form unique flower-like microstructure. Its flower-like microstructure provides a strong light absorption capacity. At the same time, the recombination of charge is inhibited, thus promoting the energy and electron transfer during the photocatalytic reaction. These properties allow reactive oxygen species to be prevalent in the reaction process of f-COFs as a photocatalyst, driving the conversion of methyl phenyl sulfide to sulfoxide within 5 h with excellent performance of 95 % conversion and 99 % selectivity.

SUPPORTED COBALT OXIDE NANOPARTICLES: THE INFLUENCE OF MESOPOROUS MATERIALS AND THEIR ROLE IMETHYL PHENYL SULFIDE OXIDATION REACTIONS.

The effect of the support in the incorporation of cobalt oxide nanoparticles on mesoporous materials (SBA‐15) and mesoporous cellular foam (MCF) was investigated. The materials were characterized using various techniques. The XRD diffraction patterns showed that the porous structures remained after cobalt incorporation, while high‐angle XRD of the MCF showed CoO peaks, in contrast to Co‐SBA‐15 which exhibited Co3O4. This was confirmed by XPS technique. The SEM‐EDS and HRTEM‐STEM microscopy indicate a distribution of cobalt oxides uniform in the samples synthesized and the average size of the particles is 1.88 nm. H2‐TPR analysis highlighted the interaction between the support surfaces and the metal oxide (SMSI). It was observed that in the SBA‐15 structure, small clusters of cobalt oxide formed with a strong interaction with silica, leading to high reduction temperatures. The catalysts activity was characterized in oxidation reactions of Methyl Phenyl Sulfide and a correlation was observed between the characterization results and the enhanced selectivity and yield towards sulfone exhibited by Co‐MCF.

Amine-functionalized activated carbon for 2-chloroethyl phenyl sulphide (2-CEPS) sensing using a portable electrochemical circuit

In this study, activated carbon (AC) is synthesized from waste thermocol sheets and functionalized it with amine groups to enhance the surface properties and selectivity. The synthesized material is further characterized using X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and X-ray Photoelectron Spectroscopy (XPS). SEM images revealed excellent porosity, XRD confirmed AC synthesis, and FTIR and XPS verified amine functionalization. The size of particles of the synthesized material is determined to be 38.4 nm using Dynamic Light Scattering (DLS). The modified carbon is used as a working electrode in an innovative portable electrochemical sensing prototype for detecting 2-chloroethyl Phenyl Sulphide (2-CEPS). Electrochemical characterizations, including cyclic voltammetry (CV) and differential pulse voltammetry (DPV), were conducted to evaluate the electrode's performance. Studies on analyte concentration effects, calibration plots, reproducibility, and stability were also performed. The prototype demonstrated a limit of detection (LOD) of 82.89 µM and a limit of quantification (LOQ) of 251.18 µM, with a linear range of 50-300 µM. Stability tests using 150 µM of 2-CEPS at pH 6 showed consistent peak current values, indicating the device's reliability. The prototype is cost-efficient, portable, and suitable for onsite detection of 2-CEPS, with potential applications in environmental monitoring, war zones, emergency response, border security, and industrial safety.

Metalation and subsequent transformations of β-pinene

β-Pinene, unlike α-pinene, is easily and quantitatively metalated with butyllithium/TMEDA. The resulting allyllithium•TMEDA is easily isolated, with the racemic material crystallizing preferentially, even from 92 % ee solutions. The complex is indefinitely stable in C6D6, and has been fully characterized. Reaction with formaldehyde favors alkylation at the less substituted allyl position with modest regioselectivity (2:1), and the corresponding Grignard reagent (made by transmetalation with MgBr2) reacts very regioselectively at the more substituted position with formaldehyde and diphenyl disulfide (99-92 %, resp.). The two phenyl sulfide isomers are observed to equilibrate when exposed to heat or UV light. This easy metalation provides access to a versatile chiral-pool-derived allyl nucleophile.

Synthesis, Characterization, and Application of a Polyoxometalates‐Based CuII Complex for Efficient Catalytic Oxidation and Electrochemical Detection

AbstractThe development of eco‐friendly, high‐efficiency polyoxometalates (POMs) catalysts is vital for advancing catalytic oxidation and electrochemical detection in environmental protection. Herein, a POM‐based CuII‐containing complex with the molecular formula [H(4‐AP)]8[Cu2(H2O)4(P2Mo5O23)2]·8H2O (1) (4‐AP = 4‐aminopyridine) is synthesized using the hydrothermal method, and the crystal structure is determined by single X‐ray diffraction (SXRD), infrared (IR) spectroscopy, and powder X‐ray diffraction (PXRD). Structurally, complex 1 exhibits a one dimension (1D) chain arrangement, composed of CuII ions and Strandberg‐type (P2Mo5O23)6− anionic clusters. These 1D chains are further interconnected through [H(4‐AP)]+ ligands, resulting in the formation of a two dimension (2D) supramolecular network. Complex 1 serves as an outstanding heterogeneous catalyst for the oxidation of methyl phenyl sulfide (MPS), demonstrating a remarkable conversion rate of 99% for MPS and a selectivity of 98% toward methyl phenyl sulfoxide (MPSO). In addition to its catalytic capabilities, complex 1 is also employed in the electrochemical detection of FeIII and CrVI ions, with low limits of detection (LODs) at 4.92 µm for FeIII and 7.82 µM for CrVI.

A comprehensive study about functionalization and de-functionalization of MOF-808 as a defect-engineered Zr-MOFs for selective catalytic oxidation

In metal–organic frameworks (MOFs), confined space as a chemical nanoreactor is as essential as coordinatively unsaturated metal site catalysis. The properties of MOFs can be adjusted through the incorporation of functional groups and open metal sites in frameworks that can modify the catalytic performance. In this regard, a set of defect-engineered MOFs, Ex-MOF-808(NH2, NO2, H) and Mix-MOF-808(NH2, NO2, H), were synthesized by ultrasonic-assisted linker exchange approach (Ex-MOFs) and solvothermal mixing ligand method (Mix-MOFs), respectively. Further, the relationship between the preparation method, structural properties, and catalytic efficiency of the prepared materials in the selective oxidation of methyl phenyl sulfide (MPS) has been investigated. By analyzing zeta potential, it was found that in the exchange method, the amount of defect and functional groups on the surface of MOFs are more than in the mixing method, which also affects the catalytic activity. In our contribution, mix-MOF-808(NO2) carrying nitro groups at their organic linkers, which has a well-dispersion of nitro groups at the framework exhibits selective conversion of MPS to sulfone (91 %). Furthermore, the performance of stable heterogeneous catalysts was investigated for three cycles, which demonstrated their great potential for advanced catalytic oxidation.

Synthesis and Characterization of 6-Ti-Substituted Polyoxomolybdate with High Catalytic Activity for Sulfide Oxidation.

A 6-Ti-substituted polyoxometalate, (NH4)5Cs7Na3H2[Cs@(Ti2GeMo10O39)3]·34H2O (1), was synthesized by reacting (NH4)6Mo7O24·4H2O, GeO2, and TiOSO4 through the conventional aqueous method. Polyanion 1a is composed of three {Ti2GeMo10} segments linked by Ti-O-Ti linkages and shows a trefoil-shaped structure. Furthermore, one Cs+ cation is encapsulated in the cavity of 1a. Notably, it possesses the highest number of Ti centers among the reported polyoxomolybdates. In addition, serving as a high-efficiency heterogeneous catalyst, 1 enables the conversion of methyl phenyl sulfide within 20 min, yielding 96.4% of the corresponding sulfoxide with good recyclability.

Modulating the Catalytic Properties of Polyoxovanadates with Transition-Metal-Complex Units for Selective Oxidation of Sulfides.

Selective oxidation of sulfides to sulfoxides is of great significance in the synthesis of pharmaceuticals, desulfurization of fuels, and detoxification of sulfur mustard chemical warfare agents. Designing selective catalysts to achieve the efficient transformation of sulfides to sulfoxides is thus highly desired. Herein, we report three transition metal-complex-functionalized polyoxovanadates, [Zn2(BPB)2][V4O12]·0.5BPB·H2O (1), [Ni(BPB)(H2O)][V2O6]·2H2O (2), and [Co(HBPB)2][V4O12] (3) (BPB = 1,4-bis(pyrid-4-yl)benzene)), and explore their applications for selective oxidation of sulfides using H2O2 as an oxidant. All three compounds were catalytically effective for the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide, with 1 being best-performing with complete conversion and a selectivity of 96.7%. In the selective oxidation of a series of aromatic and aliphatic sulfides to corresponding sulfoxides, 1 also showed satisfactory performance; in particular, the chemical warfare agent stimulant 2-chloroethyl ethyl sulfide can be completely and selectively oxidized to the nontoxic 2-chloroethyl ethyl sulfoxide within 20 min at room temperature. Catalyst 1 can be recycled and reused at least six times with uncompromised performance. The perfect performance of 1 is attributed to the synergistic effect of coordinatively unsaturated V and Zn sites in bimetallic oxide, as revealed by comparative structural and catalytic studies.

The construction of the flexible covalent organic frameworks with phenyl sulfide as linkers used for adsorping iodine and fluorescence sensing picric acid

The efficient capture of radioactive iodine and sensitive detection of picric acid are very important to environmental protection. Herein, we synthesized two new flexible 4,4′-thiodianiline (TDA)-based covalent organic frameworks (TTDA and HTDA) by using simple Schiff-base polycondensation reactions with flexible 4,4′-thiodianiline (TDA) and 2,4,6-tris(4-formylphenoxy)-1,3,5-triazine (TPT − 3 − CHO) and hexa(4-formyl-phenoxy)cyclotriphosphazene (NOP − 6 − CHO). The flexible TDA-based COFs are porous, crystalline, and show high thermal stability and good chemical stability. Due to the high content of heteroatoms, abundant aromatic rings, and orderly network, it is conducive to electron transfer, the as-prepared flexible TDA-based COFs show outstanding dual properties of iodine adsorption and fluorescence sensing. The maximum iodine capacities of TTDA and HTDA are as high as 3.34 and 4.38 g g−1, respectively. The flexible TDA-based COFs can be used for sensing picric acid with low limits of detection (LODs) of 1.25 × 10−9 and 1.67 × 10−9 mol L−1 and high quenching constants (KSV) of 6.00 × 104 and 4.88 × 104 L mol−1, respectively.

Ultraviolet Light-Assisted Decontamination of Chemical Warfare Agent Simulant 2-Chloroethyl Phenyl Sulfide on Metal-Loaded TiO2/Ti Surfaces.

The application of ultraviolet (UV) light for the decontamination of chemical warfare agents (CWAs) has gained recognition as an effective method, especially for treating hard-to-reach areas where wet chemical methods are impractical. In this study, TiO2/Ti was employed as a model catalyst, which was contaminated with 2-chloroethyl phenyl sulfide (CEPS), and subjected to photocatalytic decontamination using both UVB and UVC light. Additionally, photocatalytic decontamination efficiency by introducing Au, Pt, and Cu onto the TiO2/Ti surface was explored. During the photodecomposition process under UVC light, at least eight distinct secondary byproducts were identified. It was observed that the introduction of overlayer metals did not significantly enhance the photodecomposition under UVC light instead overlaid Au exhibited substantially improved activity under UVB light. Whereas, photodecomposition process under UVB light, only five secondary products were detected, including novel compounds with sulfoxide and sulfone functional groups. This novel study offers valuable insights into the generation of secondary products and sheds light on the roles of overlayer metals and photon wavelength in the photodecontamination process of CWA.

Tricoordinate Beryllium Radicals and Their Reactivity.

The one-electron reduction of [(CAAC)Be(Dur)Br] (CAAC = cyclic alkyl(amino)carbene, Dur = 2,3,5,6-tetramethylphenyl = duryl) with lithium sand in diethyl ether yields the first neutral, tricoordinate, and moderately stable beryllium radical, [(CAAC)(Et2O)BeDur]• (2-Et2O), which undergoes a facile second one-electron reduction concomitant with the insertion of the beryllium center into the endocyclic C-NCAAC bond and a cyclopropane-forming C-H bond activation of an adjacent methyl group. In situ generation of 2-Et2O and addition of PMe3 yield the stable analogue, [(CAAC)(Me3P)BeDur]• (2-PMe3), which serves as a platform for PMe3-ligand exchange with stronger donors, generating the radicals [(CAAC)LBeDur]• (2-L, L = isocyanides, pyridines, and N-heterocyclic carbenes). X-ray structural analyses show trigonal-planar beryllium centers and strong π backbonding from the metal to the CAAC ligand. The EPR signals of all six isolated [(CAAC)LBeDur]• radicals display significant, albeit small, hyperfine coupling to the 9Be nucleus. DFT calculations show that the spin density is mostly delocalized over the CAAC π framework and, where present, the isocyanide CN moiety, with only a small proportion (3-6%) on the beryllium center. 2-PMe3 proved thermally unstable at 80 °C, first undergoing radical hydrogen abstraction with the solvent, followed by insertion of beryllium into the endocyclic C-NCAAC bond and PMe3 transfer to the former carbene carbon atom. The reactions with diphenyl disulfide and phenyl azide occur at the beryllium center and yield the corresponding Be(II) phenyl sulfide and amino complexes, respectively, the latter concomitant with radical transfer and hydrogen abstraction by the beryllium-bound nitrogen center.

Palladium(II) complexes bearing thioether-NHC ligand: Synthesis, characterization, and their application in Suzuki-Miyaura coupling

A series of palladium(II) complexes bearing thioether-functionalized N-heterocyclic carbene ligands, namely [Pd(N-(R1,2,3)-N'-(2-(phenylthio)ethyl)-5,6-dimethylbenzimidazol-2-ylidene)Cl2(py)] (R1: 1-bromohexane, R2: 1-bromododecane, R3: 1-bromooctadecane, R’: 2-chloroethyl phenyl sulfide, py: pyridine), have been synthesized and characterized. The synthesized ligands (2a-c) and complexes (3a-c) were characterized by NMR, FT-IR, and elemental analysis. The crystal structure of Pd(II) complex 3a was determined by single-crystal X-ray diffraction. X-ray diffraction analysis revealed that the palladium ion has a slightly distorted square-planar geometry. The catalytic activity of all complexes (3a-c) for the Suzuki-Miyaura cross-coupling reaction was examined. Under the optimized conditions, aryl bromides were successfully converted into corresponding coupled products. Yields ranged high for electron-rich aryl bromides, moderate for electron-neutral bromides, and low for electron-poor bromides.

Quantum chemical modeling of enantioselective sulfoxidation and epoxidation reactions by indole monooxygenase VpIndA1.

Indole monooxygenases (IMOs) are enzymes from the family of Group E monooxygenases, requiring flavin adenine dinucleotide (FAD) for their activities. IMOs play important roles in both sulfoxidation and epoxidation reactions. The broad substrate range and high selectivity of IMOs make them promising biocatalytic tools for synthesizing chiral compounds. In the present study, quantum chemical calculations using the cluster approach were performed to investigate the reaction mechanism and the enantioselectivity of the IMO from Variovorax paradoxus EPS (VpIndA1). The sulfoxidation of methyl phenyl sulfide (MPS) and the epoxidation of indene were chosen as the representative reactions. The calculations confirmed that the FADOOH intermediate is the catalytic species in the VpIndA1 reactions. The oxidation of MPS adopts a one-step mechanism involving the direct oxygen-transfer from FADOOH to the substrate and the proton transfer from the -OH group back to FAD, while the oxidation of indene follows a stepwise mechanism involving a carbocation intermediate. It was computationally predicted that VpIndA1 prefers the formation of (S)-product for the MPS sulfoxidation and (1S,2R)-product for the indene epoxidation, consistent with the experimental observations. Importantly, the factors controlling the stereo-preference of the two reactions are identified. The findings in the present study provide valuable insights into the VpIndA1-catalyzed reactions, which are essential for the rational design of this enzyme and other IMOs for industrial applications. It is also worth emphasizing that the quantum chemical cluster approach is again demonstrated to be powerful in studying the enantioselectivity of enzymatic reactions.

Au Octahedral Nanosponges: 3D Plasmonic Nanolenses for Near-Field Focusing.

Here, we report the synthesis of three-dimensional plasmonic nanolenses for strong near-field focusing. The nanolens exhibits a distinctive structural arrangement composed of nanoporous sponge-like networks within their interior. We denote these novel nanoparticles as "Au octahedral nanosponges" (Au Oh NSs). Employing a carefully planned multistep synthetic approach with Au octahedra serving as sacrificial templates, we successfully synthesized Au Oh NSs in solution. The porous domains resembling sponges contributed to enhanced scattering and absorption of incident light within metal ligaments. This optical energy was subsequently transferred to the nanospheres at the vertex, where near-field focusing was maximized. We named this observed enhancement a "lightning-sphere effect". Using single particle-by-particle surface-enhanced Raman scattering (SERS), we optimized the morphological dimensions of the spheres and porous domains to achieve the most effective near-field focusing. In the context of bulk SERS measurements targeting weakly adsorbing analytes (2-chloroethyl phenyl sulfide) in the gas phase, we achieved a low detection limit of 10 ppb. For nonadsorbing species (dimethyl methyl phosphonate), utilization of hybrid SERS substrates consisting of Au Oh NSs and metal-organic frameworks as gas-adsorbing intermediate layers was highly effective for successful SERS detection.

Umpolung Reactivity of Diazo Arylidene Succinimides: Distal C-H Functionalization of α-Thiocarbonyls from the Reactive Carbenoid Center.

Herein, for the first time we have explored the umpolung reactivity of vinylogous carbon center of diazo arylidene succinimide (DAS) through rhodium catalysis to achieve [2,3]-Stevens rearrangement of α-thioether esters. The protocol has successfully demonstrated the distal C-H bond functionalization of the α-thioether esters. Alongside, the carbenoid reactivity of DAS has also been achieved with Doyle-Kirmse reaction of allyl/propargyl phenyl sulfides. The protocol proved to be practical to synthesize a wide variety of [2,3]-Stevens rearrangement products exclusively and the possible side products emanating from Pummerer rearrangement and [1,2]-Stevens rearrangement were not observed. This catalytic protocol works smoothly in environmentally benign solvent under open air to afford the corresponding desired products with excellent diastereo-, regio- and chemo-selectivities in good to excellent yields. The protocol also proved to be scalable on gram quantity.

Integrating Metal Complex Units and Redox Sites into Thorium‐Based Metal–Organic Frameworks for Selective Photocatalytic Oxidation of Sulfides

AbstractA series of high‐symmetry Th6–metal‐organic frameworks (MOFs) are constructed using various metal complex units and the thorium (Th) cluster, and then being applied as a well‐defined catalyst model in the photocatalytic oxidation of methyl phenyl sulfide reactions. The integration of Th6‐MOFs by incorporating metal complex units and redox sites (Th6 cluster and single‐metal site) can effectively modulate the conversion rate and selectivity. Among them, Ni–PBA–Th6 (PBA = 4‐pyridin‐4‐yl benzoic acid) achieves up to ≈99% conversion and ≈97% selectivity for methyl phenyl sulfone. Experiments and theoretical calculations further elucidate that Th6 cluster is the catalytic site for the oxidation of methyl phenyl sulfide to methyl phenyl sulfone, while Ni–PBA is the catalytic site for the reduction of hydrogen peroxide. This work sheds new insight into the structural design and photocatalytic application of more efficient thorium‐based MOF catalysts.

Light-Controlled Biocatalysis by Unspecific Peroxygenases with Genetically Encoded Photosensitizers.

Fungal unspecific peroxygenases (UPOs) have gained substantial attention for their versatile oxyfunctionalization chemistry paired with impressive catalytic capabilities. A major drawback, however, remains their sensitivity towards their co-substrate hydrogen peroxide, necessitating the use of smart in situ hydrogen peroxide generation methods to enable efficient catalysis setups. Within this report, we introduce flavin-containing protein photosensitizers as a new general tool for light-controlled in situ hydrogen peroxide production. The use of light as an abundant, inexpensive, and switchable induction agent enables efficient spatial control of enzymatic activity. By genetically fusing FbFPs and UPOs, we have created two virtually self-sufficient photo-enzymes (PhotUPO), which have been thoroughly characterized. Subsequent testing of a versatile substrate panel with the two divergent PhotUPOs revealed two stereoselective conversions. The catalytic performance of the fusion protein was optimized through enzyme and substrate loading variation, enabling up to 24300 turnover numbers (TONs) for the sulfoxidation of methyl phenyl sulfide. The PhotUPO concept was upscaled to a 100 mg substrate preparative scale, enabling the extraction of enantiopure alcohol products.