Heterogeneous Photocatalytic Strategies for C(sp³)−H Activation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 16, 2024

Abstract Activation of ubiquitous C(sp 3 )−H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers promising and sustainable approach for activation has been fast developing in the past decade. This Minireview focuses on mechanism strategies heterogeneous photocatalytic activation. After introducing mechanistic insights, including precise design active sites, regulation reactive radical species, improving charge separation reactor innovations are discussed. In addition, recent advances hydrocarbons, alcohols, ethers, amines amides by summarized. Lastly, challenges opportunities outlined to encourage more efforts development this exciting field.

Language: Английский

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Synthesis of Enantiopure Sulfoxides by Concurrent Photocatalytic Oxidation and Biocatalytic Reduction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Feb. 21, 2022

Abstract The concurrent operation of chemical and biocatalytic reactions in one pot is still a challenging task, and, particular for photocatalysts, examples besides simple cofactor recycling systems are rare. However, especially due to the complementary chemistry that two fields catalysis promote, their combination has potential unlock intriguing, unprecedented overall reactivities. Herein we demonstrate reduction photocatalytic oxidation process. Specifically, enantioselective sulfoxide using ( S )‐selective methionine reductases was coupled an unselective light‐dependent sulfoxidation. Protochlorophyllide established as new green photocatalyst Overall, cyclic deracemization process produce nonracemic sulfoxides achieved target compounds were obtained with excellent conversions (up 91 %) superb optical purity (>99 % ee ).

Language: Английский

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Exciting Enzymes: Current State and Future Perspective of Photobiocatalysis

ChemPhotoChem, Journal Year: 2023, Volume and Issue: 7(7)

Published: May 2, 2023

Abstract The recent increase of interest in photocatalysis spread to biocatalysis and triggered a rush for the development light‐dependent enzyme‐mediated or enzyme‐coupled processes. After several years intense research on photobiocatalysis, it is time evaluate state field structured manner. In this Perspective, we suggest group photobiocatalysis into distinct disciplines provide principal guidelines standards reporting photobiocatalytic results as well advice performing reactions. Overall, assess that contributes diversity biocatalytic reactions while offering selectivity enzymes photocatalysis. We foresee ongoing excitement enzymatic processes will lead discovery novel mechanisms complement with new bond‐forming additional innovative strategies utilize light possible benign energy source.

Language: Английский

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Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(37), P. 20543 - 20550

Published: July 5, 2021

Abstract Among external stimuli used to promote a chemical reaction, photocatalysis possesses unique one—light. Photons are traceless reagents that provide an exclusive opportunity alter chemoselectivity of the photocatalytic reaction varying color incident light. This strategy may be implemented by using sensitizer capable activate specific pathway depending on excitation Herein, we use potassium poly(heptazine imide) (K‐PHI), type carbon nitride, generate selectively three different products from S‐arylthioacetates simply light and otherwise identical conditions. Namely, arylchlorides produced under UV/purple, sulfonyl chlorides with blue/white, diaryldisulfides at green red A combination negatively charged polyanion, highly positive potential valence band, presence intraband states, ability sensitize singlet oxygen, multi‐electron transfer is shown enable this chromoselective conversion thioacetates.

Language: Английский

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Controlling Chemoselectivity of Catalytic Hydroboration with Light

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(8)

Published: Dec. 14, 2021

The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction a handle cross-coupling or act as mild method reducing polar functionality, these platforms rarely deal with more complex where multiple potentially reactive sites exist. Here we demonstrate, first time, use light distinguish between ketones and carboxylic acids molecules. By taking advantage different activation modes, single system can be used hydroboration, chemoselectivity dictated only by absence visible light.

Language: Английский

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Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways**

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 133(13), P. 7041 - 7045

Published: Feb. 5, 2021

Controlling the selectivity of a chemical reaction with external stimuli is common in thermal processes, but rare visible-light photocatalysis. Here we show that redox potential carbon nitride photocatalyst (CN-OA-m) can be tuned by changing irradiation wavelength to generate electron holes different oxidation potentials. This tuning was key realizing photo-chemo-enzymatic cascades give either (

Language: Английский

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8 Light-driven bioprocesses

De Gruyter eBooks, Journal Year: 2024, Volume and Issue: unknown, P. 193 - 226

Published: June 17, 2024

Enzyme catalysis and photocatalysis are two research areas that have become of major interest in organic synthesis. This is mainly because both represent attractive strategies for making chemical synthesis more efficient sustainable. Because enzyme offers several inherent advantages, such as high substrate specificity, regio-, stereoselectivity, activity under environmentally benign reaction conditions, biocatalysts increasingly being adopted by the pharmaceutical industries. In addition, has proven to be a powerful approach accessing unique reactivities upon light irradiation performing reactions with an extended range milder conditions compared light-independent alternatives. It therefore not surprising bio- photocatalytic approaches now often combined exploit exquisite selectivity enzymes transformations accessible photocatalysis. this chapter, we provide overview wide variety lightdriven bioprocesses, ranging from photochemical delivery reducing equivalents redox enzymes, cofactor regeneration, direct photoactivation enzymes. We also highlight possibility catalyzing non-natural via photoinduced promiscuity combination photo- biocatalytic used create new synthetic methodologies.

Language: Английский

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Heterogeneous Photocatalytic Strategies for C(sp³)−H Activation

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Jan. 16, 2024

Abstract Activation of ubiquitous C(sp 3 )−H bonds is extremely attractive but remains a great challenge. Heterogeneous photocatalysis offers promising and sustainable approach for activation has been fast developing in the past decade. This Minireview focuses on mechanism strategies heterogeneous photocatalytic activation. After introducing mechanistic insights, including precise design active sites, regulation reactive radical species, improving charge separation reactor innovations are discussed. In addition, recent advances hydrocarbons, alcohols, ethers, amines amides by summarized. Lastly, challenges opportunities outlined to encourage more efforts development this exciting field.

Language: Английский

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Controlling Chemoselectivity of Catalytic Hydroboration with Light

Angewandte Chemie, Journal Year: 2021, Volume and Issue: 134(8)

Published: Dec. 14, 2021

Abstract The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction a handle cross‐coupling or act as mild method reducing polar functionality, these platforms rarely deal with more complex where multiple potentially reactive sites exist. Here we demonstrate, first time, use light distinguish between ketones and carboxylic acids molecules. By taking advantage different activation modes, single system can be used hydroboration, chemoselectivity dictated only by absence visible light.

Language: Английский

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Synthesis of Enantiopure Sulfoxides by Concurrent Photocatalytic Oxidation and Biocatalytic Reduction

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(17)

Published: Feb. 21, 2022

The concurrent operation of chemical and biocatalytic reactions in one pot is still a challenging task, and, particular for photocatalysts, examples besides simple cofactor recycling systems are rare. However, especially due to the complementary chemistry that two fields catalysis promote, their combination has potential unlock intriguing, unprecedented overall reactivities. Herein we demonstrate reduction photocatalytic oxidation process. Specifically, enantioselective sulfoxide using (

Language: Английский

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