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

Chemical Reviews, Год журнала: 2022, Номер 122(9), С. 8181 - 8260

Опубликована: Март 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.

Язык: Английский

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Light-driven post-translational installation of reactive protein side chains

Nature, Год журнала: 2020, Номер 585(7826), С. 530 - 537

Опубликована: Сен. 23, 2020

Язык: Английский

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Development of a Platform for Near-Infrared Photoredox Catalysis

ACS Central Science, Год журнала: 2020, Номер 6(11), С. 2053 - 2059

Опубликована: Окт. 20, 2020

Over the past decade, chemists have embraced visible-light photoredox catalysis due to its remarkable ability activate small molecules. Broadly, these methods employ metal complexes or organic dyes convert visible light into chemical energy. Unfortunately, excitation of widely utilized Ru and Ir chromophores is energetically wasteful as ∼25% energy lost thermally before being quenched productively. Hence, methodologies require high-energy, intense accommodate said catalytic inefficiency. Herein, we report photocatalysts which cleanly near-infrared (NIR) deep red (DR) with minimal energetic waste. We leverage strong spin-orbit coupling (SOC) Os(II) photosensitizers directly access excited triplet state (T1) NIR DR irradiation from ground singlet (S0). Through strategic catalyst design, a wide range photoredox, photopolymerization, metallaphotoredox reactions usually 15-50% higher Finally, demonstrate superior penetration scalability through mole-scale arene trifluoromethylation in batch reactor.

Язык: Английский

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Progress in Photoinduced Radical Reactions using Electron Donor‐Acceptor Complexes

Asian Journal of Organic Chemistry, Год журнала: 2021, Номер 10(4), С. 711 - 748

Опубликована: Фев. 11, 2021

Abstract Photocatalyzed organic synthesis transformation is a remarkable green synthetic strategy because of the advantages operational simplicity, high chemoselectivities, cheap, and environmental benignancy, along with extensive applications in fields organic, pharmaceutical functional material chemistry. Generally, photoredox catalysts or photosensitizers are necessary for generation their excited states to perform successive oxidative reductive reactions through single electron transfer (SET) energy (ET) process. Furthermore, exploration colored donor‐acceptor (EDA) complex charge (CT) between an electron‐rich electron‐poor substrate provides chance deliver intermediate under irradiation light, resulting formation radical activate species induce various reactions. These were performed without need any external photocatalysts mild reaction conditions. Herein, this review focuses on recent progress photoinduced addition reactions, borylations, radical‐radical cross‐coupling degradation cascade cyclization via EDA complexes. We highlight these novel methodologies applications, as well mechanisms. This will help provide references medicinal chemists who charmed by photochemical transformations based

Язык: Английский

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Long wavelength–emissive Ru(II) metallacycle–based photosensitizer assisting in vivo bacterial diagnosis and antibacterial treatment

Proceedings of the National Academy of Sciences, Год журнала: 2022, Номер 119(32)

Опубликована: Авг. 1, 2022

Ruthenium (Ru) complexes are developed as latent emissive photosensitizers for cancer and pathogen photodiagnosis therapy. Nevertheless, most existing Ru limited in terms of short excitation emission wavelengths. Herein, we present an Ru(II) metallacycle (herein referred to 1) that is excited by 808-nm laser emits at a wavelength ∼1,000 nm via coordination-driven self-assembly. Metallacycle 1 exhibits good optical penetration (∼7 mm) satisfactory reactive oxygen species production properties. Furthermore, shows broad-spectrum antibacterial activity (including against drug-resistant Escherichia coli) well low cytotoxicity normal mammalian cells. In vivo studies reveal employed precise, second near-infrared biomedical window fluorescent imaging-guided, photo-triggered treatments Staphylococcus aureus-infected mice models, with negligible side effects. This work thus broads the applications supramolecular through strategy lengthening their

Язык: Английский

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Polypyridyl Ru(ii) or cyclometalated Ir(iii) functionalized architectures for photocatalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(14), С. 4725 - 4754

Опубликована: Янв. 1, 2023

The strategies of integrating the well-known photocatalysts Ru(N^N) 3 and Ir(C^N) 2 (X^N) derivatives into cavities well-defined architectures their photocatalytic properties are presented in this review.

Язык: Английский

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Single-Chain Nanoparticle Delivers a Partner Enzyme for Concurrent and Tandem Catalysis in Cells

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(10), С. 4565 - 4569

Опубликована: Фев. 26, 2020

Combining synthetic chemistry and biocatalysis is a promising but underexplored approach to intracellular catalysis. We report strategy codeliver single-chain nanoparticle (SCNP) catalyst an exogenous enzyme into cells for performing bioorthogonal reactions. The reside in endosomes, creating engineered artificial organelles that manufacture organic compounds intracellularly. This system operates both concurrent tandem reaction modes generate fluorophores or bioactive agents. combination of SCNP enzymatic catalysts provides versatile tool synthesis with applications chemical biology.

Язык: Английский

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Proximity Histidine Labeling by Umpolung Strategy Using Singlet Oxygen

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(20), С. 7726 - 7731

Опубликована: Апрель 27, 2021

While electrophilic reagents for histidine labeling have been developed, we report an umpolung strategy functionalization. A nucleophilic small molecule, 1-methyl-4-arylurazole, selectively labeled under singlet oxygen (1O2) generation conditions. Rapid can be applied instant protein labeling. Utilizing the short diffusion distance of 1O2 and a technique to localize generator, photocatalyst in close proximity ligand-binding site, demonstrated antibody Fc-selective on magnetic beads functionalized with ruthenium Fc ligand, ApA. Three residues located around ApA binding site were identified as sites by liquid chromatography–mass spectrometry analysis. This result suggests that 1O2-mediated reaction nanometer scale.

Язык: Английский

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Bioorthogonal Photocatalytic Decaging-Enabled Mitochondrial Proteomics

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(44), С. 18714 - 18720

Опубликована: Окт. 28, 2021

Spatiotemporally resolved dissection of subcellular proteome is crucial to our understanding cellular functions in health and disease. We herein report a bioorthogonal photocatalytic decaging-enabled proximity labeling strategy (CAT-Prox) for spatiotemporally mitochondrial profiling living cells. Our systematic survey the photocatalysts has led identification Ir(ppy)2bpy as mitochondria-targeting catalyst that allowed photocontrolled, rapid rescue azidobenzyl-caged quinone methide highly reactive Michael acceptor proximity-based protein mitochondria live Upon careful validation through vitro labeling, specificity, situ catalytic activity well tagging, we applied CAT-Prox Hela cells hard-to-transfect macrophage RAW264.7 with approximately 70% specificity observed from up 300 proteins enriched. Finally, was further dynamic upon lipopolysaccharide stimulation. By integrating decaging chemistry offers general, catalytic, nongenetic alternative enzyme-based strategies diverse cell settings.

Язык: Английский

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Metal complexes for catalytic and photocatalytic reactions in living cells and organisms

Chemical Science, Год журнала: 2022, Номер 14(3), С. 409 - 442

Опубликована: Дек. 2, 2022

This review presents discrete metal complexes that catalyse or photocatalyse reactions within living cells organisms.

Язык: Английский

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