Article
Chemistry, Multidisciplinary
Lucas K. Johnson, Griffin L. Barnes, Sebastian A. Fernandez, Christopher D. Vanderwal
Summary: A radical/polar crossover annulation between allyl-substituted arenes and electron-deficient alkenes is reported. This reaction generates functionalized tetralin products via Co-catalyzed hydrogen atom transfer (HAT), avoiding hydrofluorination, hydroalkoxylation, hydrogenation, alkene isomerization, and radical polymerization reactions. The mild reaction conditions tolerate various functional groups, exhibiting broad substrate scope and enabling the rapid assembly of complex tetralins, which are difficult to access through traditional Diels-Alder cycloadditions of styrenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Kasturi Ganguli, Natalia Belkova, Sabuj Kundu
Summary: In this study, new ligands containing an indolyl fragment and phenanthroline, as well as their corresponding Ru(ii) complexes, were synthesized and characterized. The catalytic activity of these cyclometalated (NNC)Ru(ii) complexes towards the beta-methylation of alcohols using methanol as the reagent was investigated. The results showed that these complexes exhibited superior reactivity compared to various (NNN)Ru(ii) complexes. They selectively methylated a wide range of primary, secondary, and aliphatic straight chain alcohols. This methodology was also applied to the methylation of natural products and the gram scale synthesis of beta-methylated alcohols.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Xiaoyi Zhang, Shen Ning, Yi Li, Yanjiao Xiong, Xuesong Wu
Summary: A synergetic catalytic system utilizing organophotocatalyst 4CzIPN, thianthrene, and methanol was developed for visible-light-induced Giese reactions of various alkanes and alkenes. The use of alkoxy radicals as hydrogen atom transfer reagents allows the reaction to proceed under mild conditions, providing alkylated products in moderate to excellent yields without the need for strong oxidants and transition metal reagents. The success of this approach relies on the in situ thianthrenation of methanol by thianthrene radical cation, triggering the generation of methoxy radical.
Article
Chemistry, Physical
Kasturi Ganguli, Adarsha Mandal, Manoj Pradhan, Ankit Kumar Deval, Sabuj Kundu
Summary: The selective synthesis of all possible products using a single catalyst and substrate under varying reaction conditions is a unique challenge and exciting area to explore. A cyclometalated (NNC)Ru(II) complex catalyzed the selective transformation of various ketones into their corresponding alcohols, beta-methylated alcohols, and alpha-methylated ketones using methanol. By adjusting the reaction parameters, it was possible to achieve the selective synthesis of all probable products. The role of different ancillary ligands coordinated to the Ru(II) center was investigated.
Article
Chemistry, Physical
Alberto Luridiana, Daniele Mazzarella, Luca Capaldo, Juan A. Rincon, Pablo Garcia-Losada, Carlos Mateos, Michael O. Frederick, Manuel Nuno, Wybren Jan Buma, Timothy Noel
Summary: A strategy for both cross-electrophile coupling and 1,2-dicarbofunctionalization of olefins has been developed. Carbon-centered radicals are generated from alkyl bromides by catalysis and silyl radical-induced halogen atom transfer (XAT) and are subsequently intercepted by a nickel catalyst to forge the targeted C(sp3)-C(sp2) and C(sp3)-C(sp3) bonds. The mild protocol is fast and scalable using flow technology, displays broad functional group tolerance, and is amenable to a wide variety of medicinally relevant moieties. Mechanistic investigations reveal that the ketone catalyst, upon photoexcitation, is responsible for the direct activation of the silicon-based XAT reagent (HAT-mediated XAT) that furnishes the targeted alkyl radical and is ultimately involved in the turnover of the nickel catalytic cycle.
Article
Chemistry, Physical
Alberto Luridiana, Daniele Mazzarella, Luca Capaldo, Juan A. Rincon, Pablo Garcia-Losada, Carlos Mateos, Michael O. Frederick, Manuel Nuno, Wybren Jan Buma, Timothy Noel
Summary: A strategy for both cross-electrophile coupling and 1,2-dicarbofunctionalization of olefins has been developed. This strategy involves the generation of carbon-centered radicals from alkyl bromides and the formation of targeted bonds using a nickel catalyst. The method is mild, fast, and applicable to a wide range of functional groups.
Article
Chemistry, Physical
Ramesh Jarupula, Saurabh Khodia, Muhammed Shabeeb, Surajit Maity
Summary: This article provides experimental evidence and computational calculations of excited state 'solvent-to-chromophore' proton transfer (ESPT) in the isolated gas phase PBI-CH3OH complex. Resonant two-colour two-photon ionization spectroscopy (R2PI) was used to determine the energy barrier of the photo-excited process. The ESPT process was confirmed by the vibrational transitions observed in the spectra of the PBI-CH3OH and PBI-CH3OD complexes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Energy & Fuels
Nini Zhang, Sheng-Li Chen, Ruyue Zhu, Wei Sun
Summary: Besides formaldehyde, acetaldehyde and acetone are also formed in the methanol-to-olefins (MTO) conversion. Acetaldehyde promotes the formation of aromatic species and leads to catalyst deactivation, while acetone has little effect on catalyst lifetime and product distribution.
Article
Chemistry, Multidisciplinary
Katrin Warm, Alice Paskin, Uwe Kuhlmann, Eckhard Bill, Marcel Swart, Michael Haumann, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: In this study, a novel S=2 oxoiron(IV) species supported by a unique ligand was generated and characterized. This species exhibited high reactivity in hydrogen atom abstraction reactions and demonstrated a unique oxidative mechanism. Complex 2 can serve as an excellent electronic and functional model for biological oxoiron(IV) intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Amaan M. Kazerouni, Daniel S. Brandes, Cassondra C. Davies, Laura F. Cotter, James M. Mayer, Shuming Chen, Jonathan A. Ellman
Summary: In this study, a photoredox-mediated hydrogen atom transfer approach was developed for the epimerization of delta-lactams to access the more stable anti diastereomers. The method exhibited broad functional group compatibility and the observed diastereoselectivities were consistent with the calculated relative stabilities. Deuterium labeling and luminescence quenching studies provided further insights into the reaction mechanism.
Article
Chemistry, Multidisciplinary
Peng Ji, Xiang Meng, Jing Chen, Feng Gao, Hang Xu, Wei Wang
Summary: Photoredox mediated single electron transfer (SET) oxidation can reversely activate electron rich aromatics, enabling their dearomatization under mild conditions. This method offers high selectivity for the dearomatization and functionalization of electron rich heteroarenes.
Article
Chemistry, Multidisciplinary
Qing Liu, Linhong Long, Pengchen Ma, Yingjie Ma, Xuebing Leng, Jie Xiao, Hui Chen, Liang Deng
Summary: An isolable iron(IV) imido complex with trifluoromethyl on nitrogen, [(IPr)Fe(NC(CF3)(2)Ph)(2)], was reported, demonstrating long Fe-N(imido) bonds, bent Fe-N(imido)-C(imido) alignments, and the ability to undergo intramolecular C-H bond activation reaction to transform into an iron(II) amido complex. Theoretical study suggests a hydrogen-atom-abstraction mechanism in the C-H bond activation reaction with low activation barrier due to the electron-withdrawing nature of the trifluoromethyl group.
CELL REPORTS PHYSICAL SCIENCE
(2021)
Review
Chemistry, Multidisciplinary
Sebastian Engl, Oliver Reiser
Summary: Atom transfer radical addition (ATRA) reactions are important transformations in synthetic chemistry for the difunctionalization of alkenes using simple starting materials. The recent advancement in photocatalysis, particularly using copper complexes, has provided a mild and energy-efficient alternative to the traditional methods that required toxic initiators or harsh thermal conditions. Copper photocatalysis has the advantage of enabling ligand exchange and facilitating transformations utilizing their coordination sphere. It also allows the access to two-component and three-component ATRA reactions that were not feasible with other catalysts like ruthenium or iridium. This review highlights the emerging field of using Cu(i)-substrate assemblies as active photocatalysts for achieving three-component coupling reactions under enantioselective control.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Xiaowei Chen, Wenhui Wei, Chunyang Li, Hongwei Zhou, Baokun Qiao, Zhiyong Jiang
Summary: A modular strategy was reported for accessing remote fluoroalkylated azaarene derivatives and alpha-deuterated analogues, isosteres of many pharmaceutically important compounds. Transformations under sustainable photoredox catalysis platform efficiently yielded valuable products with high yields and substantial deuterium incorporation. The work demonstrated the viability of hydrogen atom transfer of the alpha-sp(3) C-H of electron-withdrawing azaarenes with alkyl radicals.
Article
Chemistry, Physical
Michael Stadlhofer, Bernhard Thaler, Markus Koch
Summary: In this study, femtosecond pump-probe photoionization experiments were conducted on indium dimers solvated in helium nanodroplets. The results show detachment of ions from the droplet, indicating fragmentation of the indium dimers. The mechanism of ion formation was identified through correlation detection.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Guillaume Povie, Sankar Rao Suravarapu, Martin Peter Bircher, Melinda Meyer Mojzes, Samuel Rieder, Philippe Renaud
Article
Chemistry, Multidisciplinary
Nicholas D. C. Tappin, Weronika Michalska, Simon Rohrbach, Philippe Renaud
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Lars Gnaegi, Severin Vital Martz, Daniel Meyer, Robin Marc Schaerer, Philippe Renaud
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Biochemistry & Molecular Biology
Nicolas Millius, Guillaume Lapointe, Philippe Renaud
Article
Chemistry, Multidisciplinary
Emy Andre-Joyaux, Andrey Kuzovlev, Nicholas D. C. Tappin, Philippe Renaud
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Applied
Nicholas D. C. Tappin, Philippe Renaud
Summary: An improved procedure for halogen atom and chalcogen group transfer radical additions is reported, utilizing the thermal decomposition of DTBHN to produce reactive methyl radicals. This initiation method generates gaseous or volatile byproducts for easy purification, with simple reaction conditions and broad scope of application demonstrated. Additionally, an alternative source of radicals, DTBPO, is also shown to be effective under identical conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Elena Pruteanu, Nicholas D. C. Tappin, Vladilena Girbu, Olga Morarescu, Fabrice Denes, Veaceslav Kulcitki, Philippe Renaud
Summary: The modification of highly oxygenated forskolin and two less functionalized model substrates was investigated via intermolecular carbon-centered radical addition, leading to highly regio- and reasonably stereoselective iodine atom transfer radical addition reactions. Unexpected cyclic ether derivative was obtained from unprotected forskolin, while in situ protection of the 1,3-diol moiety as a cyclic boronic ester occurred during the iodine ATRA process by changing the mode of radical process initiation. This mild radical-mediated in situ protection of 1,3-diol may have broad applications in radical and non-radical transformations.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Lars Gnaegi, Remo Arnold, Florence Giornal, Harish Jangra, Ajoy Kapat, Erich Nyfeler, Robin M. Schaerer, Hendrik Zipse, Philippe Renaud
Summary: The stereoselectivity and stereospecificity of the triflate-mediated intramolecular Schmidt reaction of substituted 3-(1-azidocyclohexyl)propanol derivatives leading to octahydro-1H-pyrrolo[1,2-a]azepine has been studied. Chiral alcohols are converted to the azabicyclic derivative with limited racemization, and the diastereoselectivity is controlled by the initial asymmetric alcohol center. The concise synthesis of two alkaloids found in the venom of workers of the ant Myrmicaria melanogaster is reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Elena Pruteanu, Vladilena Girbu, Nicon Ungur, Leentje Persoons, Dirk Daelemans, Philippe Renaud, Veaceslav Kulcitki
Summary: A convenient molecular editing strategy based on radical mediated C-C bond formation has been developed for modification of available ent-kauranic natural scaffolds. The study shows that this strategy can lead to the synthesis of extended diterpenes with broad structural diversity and artificial diterpene-alkaloid hybrids, some of which exhibit significant cytotoxicity and promising selectivity indexes. These findings provide a solid foundation for further research on the synthesis of derivatives based on available natural product templates.
Article
Chemistry, Multidisciplinary
Eloise Colson, Julie Andrez, Ali Dabbous, Fabrice Denes, Vincent Maurel, Jean-Marie Mouesca, Philippe Renaud
Summary: A mild and simple synthesis method using visible-light photoredox catalysis is reported in this study, which provides valuable bicyclic alkaloid skeletons with high yields and high diastereoselectivity from readily available starting materials. This method is of great significance for medicinal chemistry research.
COMMUNICATIONS CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ali Dabbous, Eloise Colson, Debargha Chakravorty, Jean-Marie Mouesca, Christian Lombard, Sylvain Caillat, Jean-Luc Ravanat, Fabien Dubois, Fabrice Denes, Philippe Renaud, Vincent Maurel
Summary: The feasibility of generating alpha-aminoalkyl free radicals using various Quantum Dots (QDs) was experimentally demonstrated. QDs such as CdS core, CdSe core, and inverted type I CdS-CdSe core-shell were found to be efficient photocatalysts for a radical [3+3]-annulation reaction, leading to the formation of tropane derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Gulsana Sissengaliyeva, Fabrice Denes, Vladilena Girbu, Veaceslav Kulcitki, Elena Hofstetter, Philippe Renaud
Summary: The direct hydroperfluoroalkylation of unactivated alkenes using iodoperfluoroalkanes and 4-tert-butylcatechol as a hydrogen source has been achieved at room temperature. Hydrotrifluoromethylation can also be achieved using gaseous trifluoromethyl iodide. Additionally, a simple two-step, one-pot hydrotrifluoromethylation process using trifluoromethanesulfonyl chloride as a trifluoromethyl radical source has been developed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Luca Vedani, Manuel Gnagi-Lux, Fabrice Denes, Philippe Renaud
Summary: In this study, the preparation of polysubstituted bicyclo[3.1.0]hexanes from substituted pent-4-en-1-ylboronic acid esters was investigated. The key steps involve Matteson homologation and intramolecular cyclopropanation. By converting pinacol boronic esters to catechol boronic esters, enantioenriched bicyclo[3.1.0]hexanes can be synthesized using chiral-auxiliary control or sparteine-controlled enantioselective boroalkylation of alcohols.
Article
Chemistry, Multidisciplinary
Samuel Rieder, Camilo Melendez, Fabrice Denes, Harish Jangra, Kleni Mulliri, Hendrik Zipse, Philippe Renaud
Summary: The study describes the monoalkylation of N-methoxypyridinium salts with alkyl radicals generated from alkenes, alkyl iodides, and xanthates. The reaction proceeds under neutral conditions without the need for external oxidants, demonstrating high reactivity of methoxypyridinium salts towards radicals. It has been applied for the synthesis of unique pyridinylated terpenoids and extended to a three-component carbopyridinylation of electron-rich alkenes.
Article
Chemistry, Multidisciplinary
Qi Huang, Sankar Rao Suravarapu, Philippe Renaud
Summary: A general method has been developed for the hydroalkylation of electron-rich alkenes, showing high efficacy due to favorable polar effects and achieving good stereoselectivity control in chiral compounds.