Article
Chemistry, Multidisciplinary
Jingran Zhang, Ayesha Jalil, Jiaxin He, Zhenyang Yu, Yifu Cheng, Guangchen Li, Yunfei Du, Kang Zhao
Summary: A series of alkoxylated isobenzofuranones were conveniently synthesized through a cascade reaction. The reaction mechanism involves lactonization, aryl migration, and alkoxylation processes, and organocatalytic and chiral reactions were also explored.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Kuantao Mao, Leiyang Lv, Zhiping Li
Summary: An efficient and selective transformation of 2,2,2-trifluoroethylcarbonyls into ureas/amides with amines has been reported. This reaction allows the selective cleavage of the C-C bond of 2,2,2-trifluoroethylcarbonyls under transition metal-free and oxidant-free conditions, which is different from the functionalization of the analogous C-F or C-CF3 bond. The reaction demonstrates the unexplored reactivity of 2,2,2-trifluoroethyl carbonyls and shows a broad substrate range and good functional group tolerance.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kai Yang, Yukang Wang, Sanzhong Luo, Niankai Fu
Summary: In this study, we developed an electrophotochemical metal-catalyzed protocol for direct asymmetric decarboxylative cyanation of aliphatic carboxylic acids. By utilizing the synergistic merging of electrophotochemical cerium catalysis and asymmetric electrochemical copper catalysis, mild reaction conditions were achieved for the formation and utilization of carbon-centered radicals. This environmentally benign method smoothly converts a diverse array of arylacetic acids into the corresponding alkyl nitriles in good yields and enantioselectivities without using chemical oxidants or pre-functionalization of the acid substrates and can be readily scaled up.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jan Brauer, Elisabeth Quraishi, Lisa Marie Kammer, Till Opatz
Summary: This method utilizes Hantzsch ester as a photoreductant and nickel catalyst to couple various radicals with aryl and alkyl acyl groups. The reaction proceeds under mild conditions without the need for toxic metal reagents or bases, showing wide applicability in pharmaceuticals and complex molecular architectures.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Xanath Ispizua-Rodriguez, Socrates B. Munoz, Vinayak Krishnamurti, Thomas Mathew, G. K. S. Prakash
Summary: This method involves the synthesis of trifluoromethyl and difluoromethyl ketones from carboxylic acids using an acyloxyphosphonium ion as the active electrophile, showing tolerance to various functional groups and applicability to late-stage functionalization of pharmaceutical compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Applied
Qin Zhou, Xuanming Gong, Guobing Yan
Summary: Azo compounds have been a topic of great interest in recent decades due to their unique properties. The free radical strategy has been widely used for the chemical transformations of azobenzenes and dialkyl azodicarboxylates, particularly for hydrogenation and functionalization of N=N double bonds, as well as N-functionalization reactions via cleavage of N=N double bonds. In this review, we provide a systematic summary of these reactions and discuss their underlying mechanisms.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Xinrui Xiao, Cheng Guan, Jie Xu, Weijun Fu, Lei Yu
Summary: Selective reactions of carbonyl derivatives present challenges due to the multiple reaction sites in substrates and versatile reaction types. The rapid progress in selenium catalysis has allowed for the synthesis of useful compounds under mild and green conditions, contributing to advancements in green chemistry and safety considerations in the field.
Article
Chemistry, Organic
Jiwei Wu, Haowen Shi, Jianguo Liu, Ruiyou Wang, Jie Zhou, Xiao-Lan Xu, Hua-Jian Xu
Summary: We have developed a facile and novel electrochemical oxidative C(sp(3))-H/O-H cross-coupling method, which enables the synthesis of various useful α-acyloxyketones with moderate to excellent yields under transition metal- and oxidant-free conditions. A wide range of carboxylic acids including aromatic and aliphatic acids, as well as ketones, are compatible with this reaction.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Corey A. Baldasare, Paul G. Seybold
Summary: A quantitative structure-activity relationship (QSAR) for estimating the pK(a)s of alcohols in aqueous solution was described using density functional theory computations. High quality QSAR equations were obtained for both gas-phase Gibbs energy changes and aqueous pK(a)s. The aqueous equation could also be used to estimate the pK(a)s of other compounds.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Dezhi Lin, Hongyu Yang, Xiao Zhang, Huaming Sun, Xuepeng Zhang, Yajun Jian, Weiqiang Zhang, Yunfang Liu, Ziwei Gao
Summary: In this study, a highly selective C-O activation approach using superactive triazine esters and organoborons as coupling partners was developed for the synthesis of α,β-unsaturated ketones with diverse functional groups. Mechanistic investigation revealed that the dual function of triazine for activating the C-O bond and stabilizing non-covalent interactions between the catalyst and substrate is critical for the reaction's success. The method's efficiency, functional group compatibility, and unique mechanism make it a valuable alternative to classic methods.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Pinku Tung, Anne Schuhmacher, Philipp E. Schilling, Jeffrey W. Bode, Neal P. Mankad
Summary: This method enables the easy preparation of various types of KATs and is compatible with a variety of functional groups, such as alkenes, esters, halides, nitriles, etc.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zhihong Zhu, Xiang Chen, Shanshan Liu, Jianjun Zhang, Xiao Shen
Summary: The paper presents a simple one-pot-two-step process for the synthesis of 1-difluoromethyl 1,4-diketones through Mn-catalyzed radical Brook rearrangement. The methodology can also be used for the synthesis of 1-trifluoromethyl 1,4-diketones. The resulting products can be efficiently converted to fluoroalkyl substituted furans, thiophenes, pyrroles, and pyridazines, which are important structural motifs in natural products and pharmaceuticals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xinyu Zhang, Jinli Zhang, Jie Chen, Banghua Zhou, Jian Zhang, Shunhong Chen, Jian Wu, Yaojia Jiang
Summary: An efficient and straightforward synthetic method for constructing trifluoromethyl 2H-thiophenes through [4 + 1] cycloaddition of enaminothiones with trifluoromethyl N-tosylhydrazones has been disclosed. The cycloaddition platforms were found to be compatible with a broad substrate scope and to show high regio- and stereo-selectivities under very mild reaction conditions such as room temperature, neutral media and low loading of catalyst.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Environmental Sciences
Mohammednoor Altarawneh, Mansour H. Almatarneh, Bogdan Z. Dlugogorski
Summary: The study focuses on the thermal transformation of perfluoropentanoic acid in gas-phase reactions, constructing a gas-phase submodel with 56 reactions and 45 species. Theoretical estimates for the operation of PFAS thermal destruction systems were provided based on the formation of small fluorocarbon compounds in a specific temperature window and residence time.
Article
Chemistry, Organic
Chris M. Seong, Annabel Q. Ansel, Courtney C. Roberts
Summary: The construction of alkyl-alkyl bonds is an important tool in organic synthesis. In this study, a photocatalytic coupling of carboxylic acids to form bibenzyls was reported. The redox-opposite relationship between carboxylic acids and their redox-active esters was explored for the first time, providing mechanistic insights and potential applications in catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lisa-Marie Altmann, Viviane Zantop, Pia Wenisch, Nina Diesendorf, Markus R. Heinrich
Summary: Metal and catalyst-free carbohydroxylations and carboetherifications have been achieved at room temperature through the combination of high aryl diazonium concentration and visible light irradiation. The weak charge transfer interactions between diazonium salt and alkene significantly influence the reaction course, offering potential for aryldiazonium-based radical arylations without the need for a photocatalyst or particular additive.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Oliver Fischer, Markus R. Heinrich
Summary: 2-fluoro-5-nitrophenyldiazonium tetrafluoroborate is a novel Sanger-type reagent that enables the versatile functionalization of primary and secondary aliphatic alcohols. The diazonium unit on the resulting aryl-alkyl ether can be used for diverse transformations such as radical C-H activation, cyclization, and palladium catalyzed cross-coupling reactions, based on mild nucleophilic aromatic substitution under unprecedented, base-free conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Susanne Gradl, Johannes Koeckenberger, Janina Oppl, Martin Schiller, Markus R. Heinrich
Summary: The synthesis of pyridazinium salts from readily available phenylazosulfonates is achieved in a single reaction step. This reaction involves the formation of short-lived phenyldiazenes, which are partially protonated under strongly acidic conditions, and undergo a rapid cycloaddition to furans to give pyridazinium salts via elimination of water. Despite the presence of phenyldiazenes as intermediates, the pyridazinium synthesis shows low sensitivity toward oxygen due to the very fast cycloaddition step and partial protonation of the phenyldiazene.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ryan Thurston, Viviane Zantop, Kristen Sodam Park, Harald Maid, Anke Seitz, Markus R. Heinrich
Summary: In this study, we have presented the first examples of reversible pH-dependent switching from full trans to full cis by exploiting the effects of steric demand and the interaction of the amide carbonyl with a positive charge.
Review
Chemistry, Organic
Nina Diesendorf, Markus R. Heinrich
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Medicinal
Johannes Koeckenberger, Oliver Fischer, Andreas Konopa, Sebastian Bergwinkl, Susanne Muehlich, Peter Gmeiner, Roger Jan Kutta, Harald Huebner, Max Keller, Markus R. Heinrich
Summary: Two novel tool compounds, OFH5503 and OFH611, have been developed by linking fluorescent dyes and muscarinergic M-3 receptor ligands. These conjugates can be useful tools for determining binding affinities and studying receptor expression.
JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Nina Diesendorf, Pia Wenisch, Janina Oppl, Markus R. Heinrich
Summary: This article describes the functionalization of arenes and alkenes through additive-free radical reactions using highly photosensitive, fluorescein-derived diazonium salts. The unique properties of diazonium salts enable Meerwein-type carbohydroxylation of non-activated alkenes, which can be rationalized by a reaction mechanism involving forth and back electron transfer from and to the xanthene subunit of the fluorescein moiety.
Article
Chemistry, Multidisciplinary
Johannes Koeckenberger, Ryan Thurston, Caroline Sauer, Janina Oppl, Markus R. Heinrich
Summary: We report a highly efficient photocatalytic reaction using ruthenium photoredox catalysis combined with 1,2-dioxetane to trigger chemiluminescence. The blue light input in this system shows a defined inverse correlation with base-triggered, blue light emission as the output. The reliability and usefulness of the ruthenium-dioxetane system for optical storage, sensing, and ruthenium detection are demonstrated by comparing readout results through H-1 NMR and chemiluminescence with previous optical input.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Johannes Koeckenberger, Insa Klemt, Caroline Sauer, Anton Arkhypov, Viktor Reshetnikov, Andriy Mokhir, Markus R. Heinrich
Summary: Despite their synthetic potential, radical thiol-yne coupling reactions have rarely been used to functionalize biomolecules, especially in live cells. However, by exploiting the cellular conditions of mitochondria in cancer cells, we have demonstrated the selective targeting of these organelles using this reaction principle.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Fabian Grassl, Maike M. B. Konrad, Jasmin Kruell, Azra Pezerovic, Leon Zaehnle, Andreas Burkovski, Markus R. Heinrich
Summary: Multidrug-resistant bacteria pose a major threat to global health, while newly introduced antibiotics are losing their effectiveness. To gain insights into bacterial interaction with drugs, fluorescently labeled drug conjugates can be valuable tools. This study describes the preparation and evaluation of 13 new fluorescent antibiotic-Cy5 dye conjugates, highlighting the importance of tuning the dye polarity to achieve favorable properties for different applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Medicinal
Susanne Gradl, Viviane Zantop, Peter Gmeiner, Harald Huebner, Markus R. Heinrich
Summary: By using active pharmaceutical ingredients (APIs) recovered from expired drugs, Selectfluor can act as a reagent for simple fluorination and chlorination reactions on electron-rich arenes under mild conditions. Mechanistic experiments show that aromatic fluorination competes with chlorine-for-fluorine exchange on Selectfluor, resulting in aromatic chlorination. The resulting fluorinated or chlorinated APIs exhibit improved binding affinities at various receptors.
Article
Food Science & Technology
Laura Hoferer, Vera L. Rodrigues Guimaraes Abreu, Fabian Grassl, Oliver Fischer, Markus R. Heinrich, Sabrina Gensberger-Reigl
Summary: This study analyzed and quantified resveratrol and its derivatives in Franconian wines using ultrahigh-performance liquid chromatography-tandem mass spectrometry. The results showed that Franconian wines have high concentrations and good stability of resveratrol and its derivatives. This is of great significance for understanding the nutritional value and health benefits of Franconian wines.
ACS FOOD SCIENCE & TECHNOLOGY
(2023)
Article
Pharmacology & Pharmacy
Arne Gessner, Fabian Mueller, Pia Wenisch, Markus R. R. Heinrich, Joerg Koenig, Peter Stopfer, Martin F. F. Fromm
Summary: This study examines the sensitivity and specificity of endogenous biomarkers as tools for detecting drug-drug interactions mediated by renal transport proteins. Choline and trimethylamine N-oxide are identified as sensitive and specific biomarkers for OCT2/MATEs, while indoleacetyl glutamine and indoleacetic acid are found to be sensitive and specific biomarkers for renal OATs.
CLINICAL PHARMACOLOGY & THERAPEUTICS
(2023)
Article
Chemistry, Medicinal
Fabian Grassl, Leonard Bock, Alvaro Huete-Huerta Gonzalez, Martin Schiller, Peter Gmeiner, Joerg Koenig, Martin F. Fromm, Harald Huebner, Markus R. Heinrich
Summary: Based on APH199, two novel groups of D-4 subtype selective ligands were designed and evaluated, showing bias toward G(i) signaling pathway over β-arrestin recruitment compared to quinpirole. These compounds exhibited different bias profiles in terms of efficacy, potency, and GRK2 dependency, ranging from 1 to over 300 bias factors and activation from 15% to over 98% compared to quinpirole. Docking studies provided insights into the role of ECL2 and EPB in bias emergence, utilizing the diversity of functionally selective D-4 agonists.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Nataliya Archipowa, Lukas Wittmann, Johannes Koeckenberger, Fabian J. Ertl, Jakob Gleixner, Max Keller, Markus R. Heinrich, Roger Jan Kutta
Summary: This study investigated the photophysical properties of two commonly used fluorescent dyes. The results showed significant differences in fluorescence quantum yield and photostability between the dyes. Additionally, prolonged illumination led to a photocatalytic reaction between the dyes and tryptophan residues in proteins.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
