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981.
Jonas Žurauskas Dr. Soňa Boháčová Dr. Shangze Wu Dr. Valeria Butera Simon Schmid Michał Domański Dr. Tomáš Slanina Dr. Joshua P. Barham 《Angewandte Chemie (International ed. in English)》2023,62(44):e202307550
Electron-deficient acridones and in situ generated acridinium salts are reported as potent, closed-shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open-shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed-shell, neutral, diffusion-controlled photocatalysis. Brønsted acid activation of acridones dramatically increases excited state oxidation power (by +0.8 V). Upon reduction of protonated acridones, they transform to electron-deficient acridinium salts as even more potent photooxidants (*E1/2=+2.56–3.05 V vs SCE). These oxidize even electron-deficient arenes where conventional acridinium salt photooxidants have thusfar been limited to electron-rich arenes. Surprisingly, upon photoexcitation these electron-deficient acridinium salts appear to undergo two electron reductive quenching to form acridinide anions, spectroscopically-detected as their protonated forms. This new behaviour is partly enabled by a catalyst preassembly with the arene, and contrasts to conventional SET reductive quenching of acridinium salts. Critically, this study illustrates how redox active chromophoric molecules initially considered photocatalysts can transform during the reaction to catalytically active species with completely different redox and spectroscopic properties. 相似文献
982.
In Tae Kim Sang Woo Lee Tae Hyoung Kwak Jung Youl Lee Hyang Suk Park So Young Kim Chang Min Lee Hoi Eun Jung Jun‐Gill Kang Tack‐Jin Kim Hee‐Jung Kang ChangMoon Park Ronald L. Elsenbaumer 《Macromolecular rapid communications》2002,23(9):551-554
Oxidative coupling reaction of 1‐hexyl–3,4‐dimethylpyrrole affords a conjugated conducting poly(1‐hexyl‐3,4‐dimethyl‐2,5‐pyrrolylene) (PHDP), which is completely soluble in common organic solvents. The luminescence of PHDP is comparable to that of poly(N‐vinylcarbazole) (PVK), which has been widely used in electroluminescence devices. The quantum efficiency of PHDP is 2.5 times higher than that of PVK. A rationalization is presented relating the conductivity of PHDP to its polymer structure. 相似文献
983.
Po-Hsiang Tang Pamela Berilyn So Zi-Jing Lin Chia-Chun Hsieh Lee-Jene Lai Chia-Her Lin 《中国化学会会志》2023,70(5):1108-1115
This paper mainly discusses the applicability of using soft x-ray tomography technology to examine the multidimensional structure of metal–organic frameworks, such as their core-shell and hollow framework, by visually observing their corresponding images in different energy bands by different excitation energies for different elements. The results show that the use of soft x-ray tomography (SXT) can effectively observe the distribution of metals in the structure, as well as observe the type of hollow pores the metal – organic framework (MOF) possesses. This pioneering evaluation of MOFs via SXT shows excellent performance in the structure identification of multidimensional metal–organic frameworks. 相似文献
984.
Péter Angyal András M. Kotschy Ádám Dudás Dr. Szilárd Varga Dr. Tibor Soós 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202214096
A widely applicable, practical, and scalable synthetic method for efficient ene-type double oxidation of alkenes is reported via a two-step alkenyl thianthrenium umpolung/Kornblum-Ganem oxidation strategy. This chemo- and stereoselective procedure allows easy access to various α,β-unsaturated carbonyls that may be otherwise difficult or cumbersome to synthesize by conventional methods. For α-olefins, this metal-free transformation can be tuned according to synthetic needs to produce either the elusive (Z)-unsaturated aldehydes or their (E) counterparts. Moreover, this strategy has enabled streamlined synthesis of distinct butadienyl pheromones and kairomones. 相似文献
985.
Péter Angyal Kristóf Hegedüs Bence Balázs Mészáros Dr. János Daru Ádám Dudás Anna Rita Galambos Nariman Essmat Dr. Mahmoud Al-Khrasani Dr. Szilárd Varga Dr. Tibor Soós 《Angewandte Chemie (International ed. in English)》2023,62(35):e202303700
Mitragynine pseudoindoxyl, a kratom metabolite, has attracted increasing attention due to its favorable side effect profile as compared to conventional opioids. Herein, we describe the first enantioselective and scalable total synthesis of this natural product and its epimeric congener, speciogynine pseudoindoxyl. The characteristic spiro-5-5-6-tricyclic system of these alkaloids was formed through a protecting-group-free cascade relay process in which oxidized tryptamine and secologanin analogues were used. Furthermore, we discovered that mitragynine pseudoindoxyl acts not as a single molecular entity but as a dynamic ensemble of stereoisomers in protic environments; thus, it exhibits structural plasticity in biological systems. Accordingly, these synthetic, structural, and biological studies provide a basis for the planned design of mitragynine pseudoindoxyl analogues, which can guide the development of next-generation analgesics. 相似文献
986.
Krisztián Albitz Dr. Dániel Csókás Dr. Zoltán Dobi Prof. Imre Pápai Dr. Tibor Soós 《Angewandte Chemie (International ed. in English)》2023,62(13):e202216879
Prenylation is a ubiquitous late-stage modification in nature that often confers significantly improved bioactivity for secondary metabolites. While this lipophilic modification renders enhanced potency, the lipophilic tag(s) can diminish bioavailability and adversely alter drug transportation and metabolism. Thus, a functional-group-tolerant, mild, and selective late-stage C−H functionalization of prenyl tags would present a great potential in drug discovery programs but could also impact other fields, such as agrochemistry and chemical biology. Herein we report an exocyclic-strain-driven cross-metathesis reaction of prenyl tags, a formal double C−H oxidation protocol, that can be used for the selective late-stage derivatization of prenylated compounds and natural products. This methodology avoids the need for prefunctionalization of target molecules and affords ready access to an unprecedented library of oxo- and aza-prenylated complex molecules. Thus, in a broader context, this methodology extends late-stage functionalization beyond that available to nature. 相似文献