PHOTOCAT24: The Best of the First Edition DOI
Katy Medrano‐Uribe, Sara Cuadros, José J. Garrido‐González

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 18, 2024

With more than 185 attendees, PHOTOCAT24 has been a real success. The photochemical community is vital and vibrant, as the young researchers that have attending conference. help of light, we can perform unique transformations…and are sure there will be even to discover discuss in future edition. PHOTOCAT "School Photochemistry: from Photocatalysis Photobiology", summer school dedicated captivating world photochemistry, was born pressing need for an event would serve melting pot PhD students, postdocs, every corner globe. Two years effort by scientific committee (Prof. Luca Dell'Amico, Prof. Shoubhik Das, René Königs, Bartholomäus Pieber, Marcos Suero, Olalla Vázquez) organizing (Sara Cuadros, José Garrido, Giulio Goti, Daniele Mazzarella, Katy Medrano) culminated realization inaugural edition June 2024. sponsored supported Elsevier, Thieme, European Journal Organic Chemistry (EurJOC), Chemical Science (ChemSci), Communications (ChemComm), Society (EuChemS), Società Chimica Italiana (SCI), Institute Technology Austria (ISTA), Real Sociedad Española de Química (RSEQ), Gesellschaft Deutscher Chemiker (GDCh), Österreichischer (GöCH). "It took about two organize event; started selecting speakers venue arranging time such way participants, well speakers, science but also live city its beauty. Time think on new reactivity refresh their minds with art culture… Food wines part our cultural background, decided take very care these aspects", Dell'Amico said. place Padova, renowned home one world's oldest universities (founded 1222), which served perfect venue. welcomed all guests shared general information this developing project. featured participation 16 plenary 10 oral communications selected professors (Davide Audisio, Joshua-Philip Barham, Guillaume Dagousset, Sara Filgueira, Dana Králová, Manuel Plaza, Yuman Qin, Anna F. Tiefel, Songwei Wen, Juntao Ye). In first edition, participants 20 countries representing five continents attended school. Following compelling introduction chair PHOTOCAT24, Erick Carreira captivated audience his lecture Sunday, 2nd. He began summarizing remarkable work achieved group functionalization olefins, emphasizing groundbreaking contributions cobalt-based catalysis.1 Building essential contributions, he highlighted latest developments leverage photocatalytic tools within Co-catalyzed protocols. Notably, innovative strategy successfully applied photo-semipinacol rearrangement utilizing unactivated allylic alcohols, synthesis heterocycles through cycloisomerization olefins.2, 3 These advancements not only showcase potential methods pave breakthroughs synthetic chemistry. Up next, Burkhard König delivered engaging presentation titled "Better Synthesis Light," showcasing research photocatalysis at oil-water interface. emphasized how approach streamlines coupling reactions water, effectively substrates varying electron affinities.4 then revealed findings regarding formation diverse carbanion intermediates, highlighting superbasic anions generated reductive radical-polar crossover (RRPCO) process α-amino type.5 highly reactive intermediates possess capability deprotonate common polar solvents like acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, thus opening avenues novel organic transformations. second day talk Leonori. some most significant discoveries, use amine-borane reagents generation boryl radicals. enables borylation unusual selectivities halogen-atom transfer reagents.6 Then, introduced nitroarenes photo-responsive ozone surrogates undergo [3+2] cycloaddition alkenes.7 This selective conversion double bonds into carbonyl compounds when several sites present substrates. Steric effects play key role driving selectivity oxidative cleavage. next speaker Ryan Gilmour, who discussing focused discovering strategies enable alkene isomerization mediated energy processes. showed alkenyl boronates presence thioxanthone photosensitizer convenient access bioactive polyenes.8 Finally, discussed deracemization cyclopropanes enabled Al-salen catalyst acts both photocatalyst grants chiral environment process.9 After lunch, it Corinna Schindler's turn. She enlightened discussion chemistry azetidines photocycloadditions. exciting journey her discoveries aza Paterno-Büchi reaction using unexplored imine substrates, facilitate control modulation reactivity. part, Schindler pioneering 2019, she reported oximes moieties.10 symmetric 2,3,4-trisubstituted specific N-substituted nitro derivatives used alternative trinitrotoluene arose thought-provoking discussion.11 Dorota Gryko final day, focusing sustainable vitamin B12 photocatalyst. explained cobalester derivative, synthesized 2014, improved solubility properties B12.12 Specifically, compound's activity homocoupling benzyl bromide. During presentation, powerful combination Co Ni catalysis epoxides aryl halides.13 On third Rentmeister gave "Harnessing light activate mRNA translation". RosettaMatch application regulate light-dependent 5′ cap guanine-N7 methyltransferase.14 They designed, synthesized, characterized four variants demonstrated importance informatics cooperation experimental characterization create enzymes. technique utilizes analogues called FlashCaps, contain photo-cleavable group.15 Under irradiation conditions, FlashCaps release native without affecting cell viability translation process. Andrey Klymchenko fluorescence molecular probes applications sensing imaging biomembranes.16 provided perspective relationship between biology biology. design cyanine-based dyes low-affinity membrane anchor. moiety achieve efficient plasma labelling. Moreover, "barcoding" different colour codes variation ratio dyes.17 Before lunch break, Gasser us photodynamic therapy. His made development metal-based photosensitizers target various cancer lines. slogan "Can do better?" progression initial reports synthesizing studying Ru(II)-based Os(II)-based derivatives.18, 19 deliberate structural changes achieving exceptional performance continued explore integration photochemistry modern technologies. Timothy Noël effectiveness combining photoredox flow chemistry, especially field hydrogen atom (HAT).20, 21 Furthermore, automate robotic platform RoboChem, optimization scaling up photoreactions, C(sp2)−C(sp3) cross-electrophile trifluoromethylation reactions.22 addition, recent discovery audience: plan develop 3D-printed photoreactors.23 initiative aims make technology accessible easier use. cost-effective reactors designed multiple objectives, including enhancing energy-efficient batch processes, facilitating transition flow, enabling high reproducibility. Oliver Wenger presented patterns governing cage escape factor radical species. study complexes: Ru(II) Cr(III) photocatalysts.24 correlation quantum yields yield aliphatic aromatic amine donors sizes halogen atoms. closing excited state super reductants.25 significance pre-association pathway species crucial controlling photoreactivity. Kirsten Zeitler day. talk, exposed ideas rational IPN-based photocatalysts. Her involved analyzing redox potentials resulting size electronic donor moieties weakening acceptor strength.26 Additionally, NHC catalysis, crossed-acyloin reactions, products ketones photoreduction C−O bond.27, 28 demonstration photocatalysts audience. fifth Paolo Melchiorre, photoactivity organocatalytic intermediates. enamines iminium ions implemented donor-acceptor complex formation, direct photoexcitation, or merger photocatalysis, catalytic functions asymmetric domain.29 Subsequently, described results under biocatalytic conditions.30 metal-free cross-coupling HAT catalysis.31 Cristina Nevado led chemical transformations employing Truce-Smiles rearrangement. were disseminated studies carried out Nevado's utilization arylsulfinylamides obtain optically pure pharmaceutical motifs. modification, sulfonyl-based auxiliary structure, whereas steric factors dictate product's diastereoselectivity.32 learned type rearrangement: sulfinyl-smiles variant. research, discovered remote C(sp3)−H arylation.33 transformation occurs stereocontrolled migration. Ritter inspiring reactions. It safer production diazonium thiosulfate dihalocuprates.34 Even if main does involve highlights reinventing old methodologies technologies procedures replace hazardous reagents. C−H via thianthrenation persistent radical.35 Interestingly, thianthrenium salts obtained modifications example versatile Davide Bonifazi polycyclic hydrocarbons (PAH).36 theoretical study, optical gap PAH due heteroatom doping patterns. For purpose, they analyzed oxygen-based analogue anthanthrene, also, molecule, replaced C−C C−N, C−S,37 C−Se bonds. Their molecules exhibited interesting behavior. example, observed bathochromic effect nitrogen placed electron-rich positions anthanthrene-type core. affect solid state. last activities changed "Aula Nasini" Department Sciences University Padova. emblematic built 1912, honor Italian chemist Rafaello Nasini, whose research. Here, enjoyed talks sponsors, Elsevier Nature Chem. one, Dr. Giulia Moncelsi talked impressive Reaxys potentiate substances considering largest physicochemical, toxicology, bioactivity data retrosynthetic options artificial intelligence. Katherine Geogheghan details must consider publishing journals, specifically Chemistry. critical aspects writing, submission, editorial, publication topics given participant's knowledge steps research: i) search reactivities, ii) broad ceremony, prizes best poster SYNFACTS, EurJOC, ChemComm, ChemSci. We happy see award winners came around world: Álvaro Maqueda (University Oviedo, Spain), Alberto Luridiana Cagliari, Italy), Laura Kqiki (Institute Research Catalonia, Catia Nicoletti Sparascio Parma, Daniel Bím Biochemistry CAS, Czech Republic). At end six days, fantastic inspired continue searching horizons closed words attendees' extraordinary (Figure 1) committee's hard 2). Group picture PHOTOCAT24's organisers. Part staff PHOTOCAT24. school, immersed themselves atmosphere filled ranging photobiology. true highlight dynamic exchanges among postdoctoral during sessions. Photobiology" concluded hopes event, scheduled (at moment) secret location. PHOTOCAT26 promises recreate vibrant passionate photochemistry. certainly holds many surprises opportunities expanding domain. As committee, express gratitude national societies (a special mention SCI – Italiana) EuChemS, support commitment making great organizers following confident project strengthen over years, contributing shaping generations chemists…who light! authors extremely grateful sponsors ChemSci prizes. L.D. acknowledges financial Padova organization event. Ministero dell'Università (MUR, C93C22007660006, K.M.U., C93C22007640006, G.G.), Fondazione Cariparo (Starting Package C93C22008360007, K.M.U.), Marie Skłodowska-Curie Actions (SupraPhoCat, number: 101108382, J.J.G.G.), Council (ERC-Starting Grant 2021 SYNPHOCAT 101040025, S.C., D.M., L.D.). declare no conflict interest.

Язык: Английский

A Photo- and Cobalt-Catalyzed Highly Selective and Divergent Hydrofunctionalization of 1,3-Dienes with Phenols DOI Creative Commons
Yue Wang, Jun Miao, Honglin Dong

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An applicable cobalt-hydride-mediated selective, divergent hydroetherification and sequential hydroetherification/hydroarylation of 1,3-dienes with simple phenol feedstocks under a photoredox cobalt catalytic system have been developed. A variety allyl aryl ethers value-added chroman derivatives can be obtained in good to excellent yields stereoselectivity. This method not only obviates the need for extra hydrosilanes stoichiometric oxidants, thereby offering exceedingly mild conditions alkene hydroetherification, but also represents first case CoH-HAT-catalyzed double hydrofunctionalization alkenes sole nucleophile. The continuous selective bond-forming expands applications cobalt-hydride MHAT reaction provides novel approach design synthesis heterocyclic molecules.

Язык: Английский

Процитировано

1

Ligand Influence on the Performance of Cesium Lead Bromide Perovskite Quantum Dots in Photocatalytic C(sp3)–H Bromination Reactions DOI Creative Commons
Willi M. Amberg, Henry Lindner, Yeşim Şahin

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Lead halide perovskite quantum dots (LHP QDs) CsPbX3 generate immense interest as narrow-band emitters for displays, lasers, and light sources. All QD applications rely on suited engineering of surface capping ligands. The first generation LHP QDs employed oleic acid/oleyl amine have found only a limited use in photoredox catalysis. These catalysts been reported to be unstable decompose over the course reaction, thus reducing turnover numbers (TONs) limiting their synthetic ability. Herein, impact eight distinct ligands monodisperse CsPbBr3 is reported, affording thorough comprehension performance photocatalytic C–H brominations. efforts yielded operating at extremely low catalyst loadings (<100 ppb) with TONs 9,000,000 per QD. We emphasize that optimal catalytic requires increased accessibility without compromising structural colloidal integrity. Control experiments indicated well-known such Ir(ppy)3, Ru(bpy)3Cl2, or 4CzlPN are ineffective same reaction. Mechanistic studies reveal C–Br bond reduction CH2Br2 rate-limiting step likely facilitated through interaction surface. This work outlines holistic approach toward design practically useful photocatalysts out comprising structurally soft cores dynamically bound

Язык: Английский

Процитировано

1

Cobalt‐Catalyzed Photo‐Semipinacol Rearrangement of Unactivated Allylic Alcohols DOI Creative Commons
Henry Lindner, Erick M. Carreira

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Июнь 7, 2024

We report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well aromatic groups participate migrating groups, yielding variety α,α-disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, substituted arenes. operationally simple fully catalytic prescribe 1 mol % benzothiazinoquinoxaline organophotocatalyst, 0.5 Co-salen, 10 lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. showcase utility protocol in late-stage drug diversifications.

Язык: Английский

Процитировано

6

γ-Amino C(sp3)–H Functionalization of Aliphatic Amines through a Light-Driven Triple Catalysis DOI

Masanari Nakagawa,

Kazunori Nagao, Hirohisa Ohmiya

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 8005 - 8012

Опубликована: Май 9, 2024

We report intra- and intermolecular γ-amino C(sp3)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary triple catalysis, which is composed photoredox, cobalt, Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the via MHAT (metal hydride hydrogen reaction, (ii) generation through 1,6-HAT (iii) single-electron oxidation to carbocation equivalents, (iv) nucleophilic substitution with internal or external nucleophiles. As result, this afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, 1,3-aminoalcohol derivatives.

Язык: Английский

Процитировано

4

Cobalt Hydride-Catalyzed Hydroalkynylation of Alkenes with Alkynyl Trifluoroborates DOI

Meihui Guan,

Ting Yin,

Yue Wang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9294 - 9301

Опубликована: Июнь 4, 2024

A cobalt-catalyzed hydroalkynylation of alkenes with alkynyl trifluoroborates is described, proceeding through a cobalt hydride-mediated radical-polar crossover metal hydrogen-atom-transfer process. This method affords structurally diverse alkynyl-containing compounds in high yields under mild conditions and features wide substrate scope, good functional group tolerance, suitability for late-stage functionalization relatively complex natural products bioactive molecules. Expanding the scope to alkenyltrifluoroborate salts further increases utility developed methodology. approach paves an alternative route radical-involved alkynylation alkenylation reactions nucleophilic alkynyl/alkenyl reagents.

Язык: Английский

Процитировано

4

Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides DOI Creative Commons
Hongchao Liu, Xinyu Xu, Siyuan Tang

и другие.

Chemical Science, Год журнала: 2024, Номер 15(36), С. 14865 - 14871

Опубликована: Янв. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Язык: Английский

Процитировано

4

Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions DOI Creative Commons
Chang‐Yin Tan, Sungwoo Hong

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Язык: Английский

Процитировано

4

Cobalt-catalyzed enantioselective hydroetherification of alkenes and symmetric 1,3-diketones DOI

Meihui Guan,

Lihan Zhu, Yue Wang

и другие.

Chem Catalysis, Год журнала: 2024, Номер unknown, С. 101126 - 101126

Опубликована: Окт. 1, 2024

Язык: Английский

Процитировано

4

Cobalt/Photoredox Dual-Catalyzed Cross-Radical Coupling of Alkenes via Hydrogen Atom Transfer and Homolytic Substitution DOI

Yuto Yamaguchi,

Yuuki Hirata, Kosuke Higashida

и другие.

Organic Letters, Год журнала: 2024, Номер 26(23), С. 4893 - 4897

Опубликована: Июнь 5, 2024

Cobalt-catalyzed metal hydride hydrogen atom transfer (MHAT) in combination with photoredox catalysis has emerged as a powerful synthetic method, owing to its redox nature and applicability various radical precursors. Herein, we describe cross-radical coupling reaction under cobalt/photoredox dual catalysis. MHAT homolytic substitution (SH2) processes enabled Markovnikov-selective hydrobenzylation of di/trisubstituted alkenes, affording products quaternary carbon center redox-neutral manner.

Язык: Английский

Процитировано

3

Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT DOI

Yun-Nian Yin,

Bang-Sen Zhao,

Han-Yuan Liu

и другие.

Chem, Год журнала: 2024, Номер 10(10), С. 3088 - 3099

Опубликована: Июнь 19, 2024

Язык: Английский

Процитировано

3