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Předmět je rozdělen do dvou částí: první část (7 přednášek) je zaměřena na nedávný vývoj v C-H funkcionalizačních reakcích, katalýze přechodnými kovy, radikálové chemii a syntetické elektrochemii. Druhá část (5 přednášek) následuje s aktivací substratů pomocí světla. Kompletní výukové materiály budou dodány jako doplněk k přednáškám.
Poslední úprava: Navrátil Rafael, Ing., Ph.D. (27.09.2024)
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Literature sources will mainly include original research articles. Poslední úprava: Navrátil Rafael, Ing., Ph.D. (26.09.2024)
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Written exam (Zk) with score above 60%, followed by a short discussion. Poslední úprava: Navrátil Rafael, Ing., Ph.D. (26.09.2024)
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(1) Radical-based C–H activation and functionalization reactions involving hydrogen atom transfer (HAT), single electron transfer (SET) and halogen atom transfer (XAT) processes under enzymatic (heme- and non-heme iron-oxo and halogenase enzymes) and non-enzymatic conditions (biomimetic iron- and manganese-oxo catalysts, nitrogen radicals, boryl radicals, phosphorus radicals). (2) Radical metal-catalyzed cross-coupling reactions involving decarboxylative, deoxygenative and deaminative radical generation and C(sp3)–C(sp2/sp3), C(sp3)–N, C(sp3)–F and C(sp3)–CF3 bond formation. (3) Electrochemical reactions focusing on functionalization at sp3-hydridized carbons. Practical electrochemistry aspects for setting up oxidations, reductions, (doubly) decarboxylative cross-couplings and rapid alternating polarity experiments. (4) Innovative polar C–H activation, (late-stage) functionalization and cross-coupling reactions involving transition metal catalysis (Pd, Ni, Cu, Fe) combined with transient and native directing groups and weakly-coordinating bifunctional ligands. (5) C–H functionalization reactions involving phosphonium, Zincke and thianthrenium salts, and organobismuth compounds. (6) Reactions involving skeletal and peripheral molecular editing (nitrogen and carbon deletions and insertions, heterocycle interconversions, migratory modifications). (7) Micellar catalysis and its implementation in cross-coupling reactions (Suzuki, Negishi, Buchwald-Hartwig) and in other important organic reactions (peptide coupling, nucleophilic aromatic substitution). (8) Modern photochemical transformations. This lecture will focus on the use of light for cleavage and formation chemical bonds, leading to unusual and strained products, forming high energy containing molecules. Photoinduced rearrangements, transformation of common organic functional groups, retro-synthetic photochemistry and modern useful photochemical methods will be discussed. (9) Photocleavage and Photoligation. This lecture will cover photoremovable protecting groups, photoligations, photoreleasing, photoreleasing of pharmaceuticals, signalling molecules, photoactivatable fluorophores, fluorescence probes (viscosity, intercalation etc.) (10) Photoswitching. The lecture will cover photoswitches of different classes (azoarenes, diarylethenes, fulgides, spiropyranes, DASA, overcrowded alkenes and others) with different photoswitching modes (11) Mechanisms of photochemical activation. Various methods for activation of organic molecules will be discussed, such as: direct excitation, sensitization, upconversion, singlet fission, energy and electron transfer and manipulation with excited state multiplicity (e.g., intersystem crossing control). (12) Photocatalysis. Useful synthetic methods using photoredox and other modes of photochemical catalysis, including the combination with transition metal catalysis and electrolysis, will be discussed. Poslední úprava: Navrátil Rafael, Ing., Ph.D. (26.09.2024)
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This course will help you understand the principles of 1) emerging synthetic methods using electro-, photo- and chemical activation, and 2) modern photochemical processes. At the end, you will be able to: - explain the main principles of processes involving single-electron and hydrogen-atom transfer - compare radicals based on their nucleophilicity/electrophilicity, including implications for their generation and reactions - implement various C–H functionalization reactions, transition metal catalysis, radical chemistry, synthetic electrochemistry and photochemistry in the synthesis of complex organic molecules and light-responsive molecules - identify powerful retrosynthetic disconnections using radical cross-coupling reactions - understand the main principles of photoswitching and photorelease - identify photochemical reactivity of organic molecules and understand the application potential of modern synthetic methods with non-classical activation. Poslední úprava: Navrátil Rafael, Ing., Ph.D. (26.09.2024)
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