Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2752 - 2906

Опубликована: Авг. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Язык: Английский

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Elevating Photooxidation of Methane to Formaldehyde via TiO₂ Crystal Phase Engineering

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(35), С. 15977 - 15987

Опубликована: Авг. 15, 2022

Photocatalytic conversion of methane to value-added products under mild conditions, which represents a long sought-after goal for industrial sustainable production, remains extremely challenging afford high production and selectivity using cheap catalysts. Herein, we present the crystal phase engineering commercially available anatase TiO2 via simple thermal annealing optimize structure-property correlation. A biphase catalyst with (90%) rutile (10%) optimal interface concentration exhibits exceptional performance in oxidation formaldehyde reaction conditions water solvent, oxygen atmosphere, full-spectrum light irradiation. An unprecedented 24.27 mmol gcat-1 an excellent 97.4% toward is acquired at room temperature after 3 h reaction. Both experimental results theoretical calculations disclose that lengthens lifetime photogenerated carriers favors formation intermediate methanol species, thus maximizing efficiency aerobic formaldehyde. More importantly, feasibility scale-up demonstrated by inventing "pause-flow" reactor. This work opens avenue transformation economical way.

Язык: Английский

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Continuous flow mechanochemistry: reactive extrusion as an enabling technology in organic synthesis

Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4243 - 4260

Опубликована: Янв. 1, 2022

Reactive extrusion provides a scale-up opportunity to turn mechanochemical process from ball-mill into continuous flow. This tutorial review summarises some of the early ground-breaking work in this area.

Язык: Английский

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Accelerated Chemical Reaction Optimization Using Multi-Task Learning

ACS Central Science, Год журнала: 2023, Номер 9(5), С. 957 - 968

Опубликована: Апрель 13, 2023

Functionalization of C-H bonds is a key challenge in medicinal chemistry, particularly for fragment-based drug discovery (FBDD) where such transformations require execution the presence polar functionality necessary protein binding. Recent work has shown effectiveness Bayesian optimization (BO) self-optimization chemical reactions; however, all previous cases these algorithmic procedures have started with no prior information about reaction interest. In this work, we explore use multitask (MTBO) several silico case studies by leveraging data collected from historical campaigns to accelerate new reactions. This methodology was then translated real-world, chemistry applications yield pharmaceutical intermediates using an autonomous flow-based reactor platform. The MTBO algorithm be successful determining optimal conditions unseen experimental activation reactions differing substrates, demonstrating efficient strategy large potential cost reductions when compared industry-standard process techniques. Our findings highlight as enabling tool workflows, representing step-change utilization and machine learning goal accelerated optimization.

Язык: Английский

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Continuously Flow Photothermal Catalysis Efficiently CO₂ Reduction Over S‐Scheme 2D/0D Bi₅O₇I‐OVs/Cd_0.5Zn_0.5S Heterojunction with Strong Interfacial Electric Field

Small, Год журнала: 2023, Номер 19(12)

Опубликована: Янв. 1, 2023

Using CO2 , water, and sunlight to produce solar fuel is a very attractive process, which can synchronously reduce carbon convert energy into hydrocarbons. However, photocatalytic reduction often limited by the low selectivity of products poor activity. In this study, S-scheme Bi5 O7 I-OVs/Cd0.5 Zn0.5 S (Bi5 I-OVs/CZS-0.5) heterojunction with strong interfacial electric field (IEF) prepared in situ growth method. The performance CO studied continuous flow photothermal catalytic (PTC) platform. 12.5% I-OVs/CZS-0.5 shows excellent yield 58.6 µmol g-1 h-1 98.4%, are 35.1 times than that CZS-0.5 under visible light. charge transfer path through theoretical calculation (DFT), irradiation Kelvin probe force microscope (ISI-KPFM) X-ray photoelectron spectroscopy (ISI-XPS) analysis, verified. study provide useful guidance reference for improving activity oxygen vacancy induced IEF development PTC system.

Язык: Английский

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Ready, Set, Flow! Automated Continuous Synthesis and Optimization

Trends in Chemistry, Год журнала: 2021, Номер 3(5), С. 373 - 386

Опубликована: Март 7, 2021

Язык: Английский

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Nickel‐Catalyzed Electrochemical C(sp³)−C(sp²) Cross‐Coupling Reactions of Benzyl Trifluoroborate and Organic Halides**

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(11), С. 6107 - 6116

Опубликована: Дек. 8, 2020

Reported here is the redox neutral electrochemical C(sp2 )-C(sp3 ) cross-coupling reaction of bench-stable aryl halides or β-bromostyrene (electrophiles) and benzylic trifluoroborates (nucleophiles) using nonprecious, NiCl2 ⋅glyme/polypyridine catalysts in an undivided cell configuration under ambient conditions. The broad scope good yields Ni-catalyzed coupling reactions were confirmed by 50 examples aryl/β-styrenyl chloride/bromide trifluoroborates. Potential applications demonstrated electrosynthesis late-stage functionalization pharmaceuticals natural amino acid modification, three run on gram-scale a flow-cell electrolyzer. C-C proceed through unconventional radical transmetalation mechanism. This method highly productive expected to find wide-spread organic synthesis.

Язык: Английский

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Microfluidic plasmas: Novel technique for chemistry and chemical engineering

Chemical Engineering Journal, Год журнала: 2021, Номер 417, С. 129355 - 129355

Опубликована: Март 14, 2021

Язык: Английский

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Continuous flow asymmetric synthesis of chiral active pharmaceutical ingredients and their advanced intermediates

Green Chemistry, Год журнала: 2021, Номер 23(17), С. 6117 - 6138

Опубликована: Янв. 1, 2021

Catalytic enantioselective transformations provide well-established and direct access to stereogenic synthons that are broadly distributed among active pharmaceutical ingredients (APIs). These reactions have been demonstrated benefit considerably from the merits of continuous processing microreactor technology. Over past few years, flow catalysis has grown into a mature field found diverse applications in asymmetric synthesis pharmaceutically substances. The present review therefore surveys chemistry-based approaches for chiral APIs their advanced intermediates, covering utilization biocatalysis, organometallic metal-free organocatalysis introduce asymmetry continuously operated systems. Single-step processes, interrupted multistep syntheses, combined batch/flow processes uninterrupted one-flow syntheses discussed herein.

Язык: Английский

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Towards the Standardization of Flow Chemistry Protocols for Organic Reactions

Chemistry - Methods, Год журнала: 2021, Номер 1(11), С. 454 - 467

Опубликована: Сен. 13, 2021

Abstract Flow chemistry studies can sometimes be difficult to reproduce. In this article we provide guidance scientists for experimental details that should considered as part of any organic chemistry‐based continuous flow study. A focus is placed on information provided within reported enable experiments more easily and reliably reproduced. Topics covered include reactor components assembly, important parameter effects useful performance criteria. The covers aspects homogeneous systems, multiphase transformations, catalytic reactions (homogeneous heterogeneous). detailed discussion photochemistry, biocatalysis electrochemical systems outside the scope review.

Язык: Английский

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