Article
Biochemistry & Molecular Biology
Elwira Bisz
Summary: Aryl sulfonate esters are versatile synthetic intermediates due to their bioactive properties. The study introduces a method for the synthesis of alkyl-substituted benzenesulfonate esters by iron-catalyzed C(sp(2))-C(sp(3)) cross-coupling, showing high reactivity and compatibility with a broad range of substrates. The environmentally benign and sustainable iron catalytic system plays a key role in achieving high to excellent yields of the alkylated products.
Article
Multidisciplinary Sciences
Lumin Zhang, Bethany M. DeMuynck, Alyson N. Paneque, Joy E. Rutherford, David A. Nagib
Summary: Carbenes, highly reactive intermediates, are successfully generated from common aldehydes via stable alpha-acyloxy halide intermediates, enabling diverse and valuable chemistry reactions. This strategy utilizes zinc carbenoids and earth-abundant metal salts as catalysts to achieve safe and selective carbene additions to sigma and pi bonds.
Article
Chemistry, Physical
Angel Renteria-Gomez, Wes Lee, Shuai Yin, Michael Davis, Achyut Ranjan Gogoi, Osvaldo Gutierrez
Summary: This study presents a conceptually different approach to access diverse (fluoro)alkyl BCP-aryls through an iron-catalyzed multicomponent radical cross-coupling reaction. Experimental and computational mechanistic studies provide insights into the mechanism and ligand effects on C-C bond formation.
Article
Chemistry, Multidisciplinary
Quanquan Wang, Boon Chong Lee, NingXi Song, Ming Joo Koh
Summary: Stereoselective C-glycosylation reactions using bench-stable heteroaryl glycosyl sulfone donors are rare. This study presents two complementary nonprecious metal catalytic systems based on iron or nickel, capable of efficiently coupling heteroaryl glycosyl sulfones with aromatic nucleophiles or electrophiles through distinct mechanisms and modes of activation. The methods provide excellent selectivity, scope, and functional-group compatibility, allowing access to both alpha and beta isomers of key sugar residues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yipin Zhang, Xia Ge, Hongjian Lu, Guigen Li
Summary: Transition-metal-catalyzed sp(2) C-N bond formation is a reliable method for synthesizing aryl amines. This method introduces a cascade approach using organic carboxylic acids and easily prepared azidoformates as carbon and nitrogen sources, achieving high yields and minimal byproducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We present a dual catalytic strategy for the functionalization of aliphatic carboxylic acids using photoinduced iron/copper catalysts. The photoinduced ligand-to-iron charge transfer process generates an unstabilized alkyl radical, which is then utilized by the copper catalyst for coupling reactions to form C-N or C-C bonds. This system enables efficient conversion of a wide range of aliphatic carboxylic acids and has potential applications in drug discovery.
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We have developed a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. By merging iron-catalyzed decarboxylation with copper catalysis, this system allows efficient conversion of a wide range of aliphatic carboxylic acids for various reactions. The strategy has applications in compound library synthesis and the discovery of pharmaceutical agents.
Article
Chemistry, Organic
Jing-Ao Ren, Jin-He Na, Chao Gui, Chengping Miao, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A nickel-catalyzed direct cross-coupling between unactivated aryl fluorides and aryl bromides was achieved. This one-pot reaction proceeds effectively at room temperature in THF, avoiding the use of preformed and sensitive organometallic reagents. The desired biaryls are produced in modest to good yields via C-F bond cleavage in the presence of a phosphine ligand and magnesium powder (with or without TMSCl).
Article
Chemistry, Multidisciplinary
Etienne Crochet, Lucile Anthore-Dalion, Thibault Cantat
Summary: Investigation was conducted on the reactivity of alkyl formates as novel transfer hydroalkylation reagents in the transfer hydroalkylation of imines. By using a ruthenium-based catalyst and LiI as promoter to cleave the C-O sigma-bond of the formate scaffold, tertiary amines were produced with divergent regioselectivity compared to previously reported strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Atul Kumar, Gulenur N. Khatun, Rodney A. Fernandes
Summary: An efficient, mild, and economical approach for the regioselective synthesis of 4-aryl/alkyl-1-peroxy-but-3-en-2-ols from 1-substituted-1,3-butadienes using hydroperoxides and catalyzed by TBAI has been achieved. This method is simple to operate, does not require dry conditions, and has excellent tolerance to a wide range of substrates, resulting in good yields of corresponding hydroxyperoxidates. Thus, an outstanding regioselective orthogonal dioxygenation in a diene system has been accomplished.
Article
Chemistry, Multidisciplinary
Sisi Wu, Weijia Shi, Gang Zou
Summary: Liquid-assisted grinding has been successfully used to eliminate the need for chemical activators and anhydrous solvents in nickel-catalyzed, manganese-mediated cross-electrophile coupling between aryl and alkyl bromides. The optimal condition obtained through a combined evaluation of reaction and mechanical parameters allowed for the synthesis of various n-alkyl aromatics with different functional groups in good yields with a 1 mol% catalyst loading. The practical application of liquid-assisted grinding-enabled aryl/alkyl cross-electrophile coupling has been demonstrated in the gram-scale synthesis of 6-methoxytetralone.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Swantje Lerch, Stefan Fritsch, Thomas Strassner
Summary: We have developed a robust catalyst system for the Friedel-Crafts acylation of benzene derivatives in tunable aryl alkyl ionic liquids (TAAILs), by optimizing the metal salt, reaction conditions, and ionic liquids. This system tolerates different electron-rich substrates under ambient atmosphere and allows for a multigram scale.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Anthony N. Cauley, Antonio Ramirez, Chandan L. Barhate, Andrew F. Donnell, Purnima Khandelwal, Melda Sezen-Edmonds, Trevor C. Sherwood, Jack L. Sloane, Cullen L. Cavallaro, Eric M. Simmons
Summary: By utilizing quinoline as a mild catalytic additive, a broadly applicable method for Ni/photoredox-catalyzed C(sp(2))-C(sp(3)) cross-coupling was developed, which can be used in both batch and flow reactions. The method is effective for both primary benzylic nucleophiles and stabilized/nonstabilized secondary alkyl boronic esters.
Article
Chemistry, Organic
Joao V. Santiago, Katarzyna Orlowska, Michal Ociepa, Dorota Gryko
Summary: Diazo compounds with redox-active leaving groups are versatile reagents for orthogonal functionalizations, and their photochemical behavior is still to be defined. In this study, we show that under light irradiation, reactions only occur on the diazo moiety, leaving the NHPI functionality intact. Blue light can activate both aryl- and alkyl-substituted NHPI diazoacetates, leading to either C-H insertion or hydrogen/carbon 1,2-rearrangement depending on the substituent group.
Article
Chemistry, Multidisciplinary
Wen-Tao Zhao, Huan Meng, Jia-Ni Lin, Wei Shu
Summary: In this study, a ligand-controlled regiodivergent alkylation of alkyl bromides at different positions has been developed via Ni-catalyzed alkyl-alkyl cross-electrophile coupling with a second alkyl bromide. The reaction selectively isomerizes one alkyl bromide in a controlled manner, providing diverse alkylated structures at different sites. The reaction exhibits excellent chemo- and regioselectivity at three similar positions, showcasing the remarkable ligand-tuned reactivity between alkyl-alkyl cross-coupling and nickel migration. This reaction offers a catalytic platform for the synthesis of diverse saturated architectures from identical starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Debasis Koley, Sriman De, Nardana Sivendran, Lukas J. Goossen
Summary: In this study, it was found that a significant amount of products are formed via the dinuclear pathway during isomerization of allyl arenes, esters, amides, ethers, and alcohols. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Organic
Jonas F. Goebel, Zhongyi Zeng, Lukas J. Goossen
Summary: The article summarizes recent advances in the synthesis of biaryls through electrooxidative processes, with a particular focus on electrooxidative C-H/C-M couplings and dehydrogenative couplings.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Zhongyi Zeng, Jonas F. Goebel, Xianming Liu, Lukas J. Goossen
Summary: 2,2'-Biaryldicarboxylates can be conveniently accessed from benzoic acids via Rh-catalyzed electrooxidative C-H/C-H couplings, yielding valuable dihydrogen as a byproduct. RhCl3 center dot 3H(2)O catalyzes the oxidative carboxylate-directed ortho-homocoupling of various aromatic acids in an undivided cell with Pt electrodes, with a current efficiency of 67%.
Article
Chemistry, Multidisciplinary
Nardana Sivendran, Florian Belitz, Daniel Sowa Prendes, Angel Manu Martinez, Rochus Schmid, Lukas J. Goossen
Summary: This study explores the application of Trihalide salts in photochemical dediazotizing halogenations, revealing that high yields and outstanding selectivities for halogenation can be achieved without the need for metal catalysts. In addition, convenient protocols are disclosed for the brominations, iodinations, and chlorinations of diverse functionalized derivatives.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Xiao-Jing Wei, Bingxiang Xue, Jens Handelmann, Zhiyong Hu, Heidar Darmandeh, Viktoria H. Gessner, Lukas J. Goossen
Summary: In this study, a novel catalyst prYPhos was developed to promote Pd-catalyzed Suzuki-Miyaura couplings. Under mild reaction conditions, this catalyst efficiently produced various (hetero)biaryls with good tolerance towards sensitive functional groups and steric hindrance. The results demonstrated that this catalyst exhibited high selectivity in selectively coupling chlorides and leaving triflate groups intact.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ann-Katrin Seitz, Philipp J. Kohlpaintner, Tim Lingen, Marco Dyga, Fiona Sprang, Michael Zirbes, Siegfried R. Waldvogel, Lukas J. Goossen
Summary: Concentrated peroxodicarbonate solutions have been successfully prepared through electrolysis of carbonate solutions, and their synthetic potential has been demonstrated in various transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Florian Belitz, Ann-Katrin Seitz, Jonas F. Goebel, Zhiyong Hu, Lukas J. Goossen
Summary: In the presence of a [Ru(p-cymene)Cl-2](2)/triethylphosphine/lithium carbonate catalyst system, aryl bromides undergo (Z)-selective couplings with unprotected 2-arylacrylic acids to form (Z)-diarylacrylic acids. This vinylic C-H functionalization proceeds with high yields and (Z/E)-ratios, and it can tolerate a wide range of functional groups. Mechanistic studies indicate that the vinylic C-H activation proceeds via base-assisted cyclometalation and it shows orthogonal stereoselectivity.
Article
Chemistry, Organic
Ann-Katrin Seitz, Tim van Lingen, Marco Dyga, Philipp J. Kohlpaintner, Siegfried R. Waldvogel, Lukas J. Goossen
Summary: The N-oxidation of tertiary amines can be achieved using electrochemically generated peroxodicarbonate solutions. The presence of EDTA and 2,2,2-trifluoroacetophenone as mediators is crucial for converting water-insoluble substrates.
Article
Chemistry, Multidisciplinary
Dominik Lichte, Nico Pirkl, Gregor Heinrich, Sayan Dutta, Jonas F. Goebel, Debasis Koley, Lukas J. Goossen
Summary: This study demonstrates the achievement of para-C-H arylation of non-activated aryl halides with anilines using a base-assisted metalla-tautomerism approach. The challenge of directing functionalization towards the furthest C-H group has been overcome.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jonas F. Goebel, Julian Loeffler, Zhongyi Zeng, Jens Handelmann, Albert Hermann, Ilja Rodstein, Tobias Gensch, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium-catalyzed couplings of silicon enolates with aryl electrophiles are limited to expensive bromide substrates. However, a study using ylide functionalized phosphines (YPhos) showed promising results in coupling inexpensive aryl chlorides with alpha-trimethylsilyl alkylnitriles. A statistical model was developed to predict catalyst structures with superior performance, leading to the synthesis of pharmaceutically significant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jonas F. Goebel, Johanna Stemmer, Florian Belitz, Lukas J. Goossen
Summary: The 3d-metal catalyst Mn(CO)(5)Br efficiently promotes ortho C-H allylations of arenecarboxylates in the presence of neocuproine as the ligand. The selectivity of this relatively simple directing group and catalyst system surpasses the state-of-the-art, exclusively producing mono-allylated products with high selectivities for the least hindered ortho-position. The directing group can be selectively removed by in situ decarboxylation, providing a regioselective access to allyl arenes. The preparative utility of this process and its orthogonality to other approaches were demonstrated by the synthesis of 44 products with otherwise difficult substitution patterns.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tim van Lingen, Valentina Bragoni, Marco Dyga, Benjamin Exner, Daniel Schick, Christoph Held, Gabriele Sadowski, Lukas J. Goossen
Summary: This study addresses the challenge of salt waste formation in C-H carboxylations, which hinders the use of CO2 as a C-1 building block in industrial synthesis. Through a circular process, dimethyl succinate, a C-4 base chemical, is produced from CO2 and acetylene. Increased CO2 pressure allows for reversible acidification and esterification of the succinate salt, while the cesium base and hydrogenation catalyst are regenerated for reuse. Thermodynamic modeling reveals the origins of the reversible acidity switch and the crucial roles of the cesium base and NMP/MeOH solvents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Philipp J. Kohlpaintner, Lucas Marquart, Lukas J. Goossen, Siegfried R. Waldvogel
Summary: Peroxodicarbonate is a green and underexplored oxidizer generated electrochemically from aqueous carbonate solutions. With advanced electrolyzer technology, highly concentrated solutions are now accessible. These solutions have been successfully used as green oxidizers in deborolative hydroxylations, leading to the synthesis of a variety of phenols and alcohols with yields up to 99% from organoboron compounds using environmentally friendly solvents. The scalability of this transformation to multi-gram batch sizes has also been demonstrated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Applied
Bingxiang Xue, Jie Shen, Sourav Manna, Angelino Doppiu, Lukas J. Goossen
Summary: A new catalyst has been discovered that can selectively introduce a primary amino group into aromatic compounds, and it can efficiently promote the amination reaction to synthesize primary anilines within 30 minutes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
