Photocatalysis in the Life Science Industry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

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Nitrogen-Centered Radicals in Functionalization of sp² Systems: Generation, Reactivity, and Applications in Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(9), P. 8181 - 8260

Published: March 14, 2022

The chemistry of nitrogen-centered radicals (NCRs) has plentiful applications in organic synthesis, and they continue to expand as our understanding these reactive species increases. utility intermediates is demonstrated the recent advances C–H amination (di)amination alkenes. Synthesis previously challenging structures can be achieved by efficient functionalization sp2 moieties without prefunctionalization, allowing for faster more streamlined synthesis. This Review addresses generation, reactivity, application NCRs, including, but not limited to, iminyl, aminyl, amidyl, aminium species. Contributions from early discovery up most examples have been highlighted, covering radical initiation, thermolysis, photolysis, and, recently, photoredox catalysis. Radical-mediated intermolecular (hetero)arenes occur with a variety complex amine precursors, generating aniline derivatives, an important class drug development. Functionalization olefins achievable high anti-Markovnikov regioselectivity allows access difunctionalized when intermediate carbon are trapped. Additionally, reactivity NCRs harnessed rapid construction N-heterocycles such pyrrolidines, phenanthridines, quinoxalines, quinazolinones.

Language: Английский

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Emerging concepts in photocatalytic organic synthesis

iScience, Journal Year: 2021, Volume and Issue: 24(3), P. 102209 - 102209

Published: Feb. 21, 2021

Visible light photocatalysis has become a powerful tool in organic synthesis that uses photons as traceless, sustainable reagents. Most of the activities field focus on development new reactions via common photoredox cycles, but recently number exciting concepts and strategies entered less charted territories. We survey approaches enable use longer wavelengths show wavelength intensity are import parameters tuning reactivity photocatalyst to control or change selectivity chemical reactions. In addition, we discuss recent efforts substitute strong reductants, such elemental lithium sodium, by technological advances field.

Language: Английский

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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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Chromoselective Photocatalysis Enables Stereocomplementary Biocatalytic Pathways**

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(13), P. 6965 - 6969

Published: Feb. 5, 2021

Abstract 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 ( S )‐ or R )‐enantiomer phenylethanol. In combination an unspecific peroxygenase from Agrocybe aegerita , green light CN‐OA‐m led enantioselective hydroxylation ethylbenzene )‐1‐phenylethanol (99 % ee ). contrast, blue triggered photocatalytic acetophenone, which turn enantioselectively reduced alcohol dehydrogenase Rhodococcus ruber form (93

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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Red edge effect and chromoselective photocatalysis with amorphous covalent triazine-based frameworks

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: April 21, 2022

Abstract Chromoselective photocatalysis offers an intriguing opportunity to enable a specific reaction pathway out of potentially possible multiplicity for given substrate by using sensitizer that converts the energy incident photon into redox potential corresponding magnitude. Several sensitizers possessing different discrete potentials (high/low) upon excitation with photons wavelength (short/long) have been reported. Herein, we report design molecular structures two-dimensional amorphous covalent triazine-based frameworks (CTFs) intraband states close valence band strong red edge effect (REE). REE enables generation continuum excited sites characterized their own potentials, magnitude proportional photons. Separation charge carriers in such materials depends strongly on light and is primary parameter defines efficacy photocatalytic bromination electron rich aromatic compounds. In dual Ni-photocatalysis, electrons from conduction CTF 625 nm selective formation C‒N cross-coupling products arylhalides pyrrolidine, while undesirable dehalogenation process completely suppressed.

Language: Английский

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Unspecific peroxygenases: The pot of gold at the end of the oxyfunctionalization rainbow?

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2023, Volume and Issue: 41, P. 100786 - 100786

Published: Feb. 16, 2023

Fungal unspecific peroxygenases (UPOs) are among the most promising biocatalysts in synthetic chemistry. The kaleidoscope of oxyfunctionalization reactions that industrial and environmental relevance offer UPOs opportunity to provide solutions many processes. However, there important shortcomings must first be overcome order convert into applied biocatalysts, which include their general poor levels heterologous functional expression, presence unwanted peroxidase activity overoxidation reactions, as well oxidative inactivation provoked by co-substrate, hydrogen peroxide. specific engineering these proteins, they participate, is being used tackle principal challenges, with a view generate portfolio highly active, selective stable variants. In this review, we will discuss some recent developments true focusing on different trends currently followed fascinating field research.

Language: Английский

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Red Light–Blue Light Chromoselective C(sp²)–X Bond Activation by Organic Helicenium-Based Photocatalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7922 - 7930

Published: March 18, 2024

Chromoselective bond activation has been achieved in organic helicenium (nPr-DMQA+)-based photoredox catalysis. Consequently, control over chromoselective C(sp2)–X multihalogenated aromatics demonstrated. nPr-DMQA+ can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp2)–I bonds. In contrast, blue initiates consecutive photoinduced electron (conPET) more challenging C(sp2)–Br Comparative reaction outcomes have demonstrated α-arylation of cyclic ketones with and lights. Furthermore, red-light-mediated selective bonds activated iodobromoarenes keep bromo functional handle untouched. Finally, strength catalysis highlighted two-fold functionalization using both photo-to-transition metal photo-to-photocatalyzed transformations.

Language: Английский

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Wavelength-Selective C–C and C–N Bond Formation via Defect-Engineered ZnIn₂S₄

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11554 - 11563

Published: July 19, 2024

Language: Английский

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