Article
Chemistry, Organic
Yiwen Wang, Ya-Nan Tian, Shiyan Ren, Ruijie Zhu, Bin Huang, Yanqiong Wen, Shiqing Li
Summary: The homo anion-cation coupling of cyclic diaryl lambda(3)-bromanes/diarylbrominiums is reported for the first time, which has not been previously reported. Competition experiments indicate that the anion-cation coupling follows the nucleophilic ability of the anions, with higher nucleophilicity resulting in higher reactivity. Additionally, a metal-free cross-coupling reaction of cyclic diarylbrominium tosylates with various alcohols, phenols, water, and their deuterated forms has been developed under mild conditions, yielding meta-functionalized biaryl motifs in high yields with broad substrate scope. Preliminary mechanistic studies suggest that the nucleophilic agent is the main source of protons in the cross-anion-cation coupling, which is influenced by its concentration.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jinghui Zhang, Meng Zhang, Yumeng Shi
Summary: This report presents a metal-free convergent paired electrolysis strategy for the synthesis of alpha-benzyl amine from imines and methylarenes, utilizing both anodic oxidation and cathodic reduction. The key to the success of this electrolysis is the simultaneous matching of desirable half reactions, leading to the desired product.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Renxu Cao, Yu Liu, Xiaoxin Shi, Jun Zheng
Summary: alpha-amino ketones are important compounds in synthetic and medicinal chemistry. However, there are limited methods to directly access these compounds from available starting materials. This study developed a visible-light mediated reductive cross-electrophile coupling to synthesize alpha-amino ketones from easily accessible imines and anhydrides. Under mild reaction conditions, diverse imines reacted with anhydrides to give a variety of alpha-amino ketones with good yields and broad functional group compatibility. Primary mechanistic studies suggested that this transformation mainly proceeded through a radical-radical cross coupling pathway.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Zuxiao Zhang, Duong T. Ngo, David A. Nagib
Summary: A dual catalytic strategy involving an Ir photocatalyst and a Cu complex enables regioselective amination and cross-coupling of allyl alcohols with various nucleophiles. This approach allows for the formation of N-radicals via an energy transfer mechanism followed by interception of alkyl radicals for radical amino-functionalizations of olefins. Insights into the nature of Cu-based radical interception are provided through stereo, regio, and kinetic probes.
Article
Chemistry, Organic
Xiao-Wen Wang, Rui-Xue Li, Yang Deng, Ming-Qiu-Hao Fu, Ya-Nan Zhao, Zhi Guan, Yan-Hong He
Summary: This article proposes a new method for the direct hydroxylarylation of unactivated benzylic carbons (sp3/sp2/sp) without the need for pre-functionalized benzylic alcohols, aromatic aldehydes, or ketones. It features direct functionalization of unactivated benzylic C(sp3)-H bonds and benzylic sp2/sp-carbons, mild conditions (open air, room temperature), an environmentally friendly procedure (without any external catalyst/mediator/additive), and direct access to sterically hindered alcohols from inexpensive and readily available alkyl/alkenyl/alkynylbenzenes. Mechanistic studies strongly support the proposed radical-radical cross-coupling between transient ketyl radicals and persistent radical anions. Gram-scale synthesis and diversification of drug derivatives demonstrate the practical potential of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yushi Tan, Wu Xuekun, Ya-Ping Han, Yuecheng Zhang, Hong-Yu Zhang, Jiquan Zhao
Summary: An efficient and convenient method for synthesizing 6-oxyalkylated 1,2,4-triazine-3,5(2H, 4H)-diones has been developed using a visible-light-induced cross-dehydrogenative coupling reaction. This reaction allows for a wide range of functional groups and uses a cheap and low-toxic photocatalyst and air as an oxidant. Additionally, the reaction can be driven by sunlight as a clean energy resource and has demonstrated utility in gram-scale reactions and the synthesis of key intermediates for bioactive molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ayan Jati, Kaushik Dey, Maryam Nurhuda, Matthew A. Addicoat, Rahul Banerjee, Biplab Maji
Summary: This study presents a dual metalation strategy using a COF TpBpy for C-N cross-coupling reactions. The strategy demonstrates controlled metalation, recyclability, and visible-light-mediated catalysis. Experimental and theoretical studies provide insights into the catalyst and reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Stephane Sengmany, Farah Daili, Ibtihal Kribii, Eric Leonel
Summary: Arylamines are a type of compounds commonly found in natural products and pharmaceuticals. Nickel-catalyzed amination of aryl halides is often used for their synthesis, but it requires complex and expensive nickel complexes. To address this issue, an electrochemical method based on sacrificial anode process is developed to generate a catalytic amount of nickel salts, enabling the amination of aryl halides under mild reaction conditions and providing access to a wide range of arylamines.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
James M. Fordham, Philipp Kollmus, Monika Cavegn, Regina Schneider, Marco Santagostino
Summary: A screening method for rapid identification of catalytic conditions for Pd-catalyzed C-N cross-coupling reactions is presented. The method evaluates mixtures of precatalysts, ligands, and bases to identify productive conditions, and then optimizes them through deconvolution steps, uncovering the active catalyst and identifying the optimal solvent and base. The utility of this method is demonstrated through the identification of effective conditions for Pd-catalyzed cross-coupling of complex molecules, leading to the discovery of new chemical reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Rie Fujita, Kengo Hanaya, Takeshi Sugai, Shuhei Higashibayashi
Summary: The hydroquinoline skeleton of symbioimine was constructed by Cu-mediated N-alkenylation or O-alkenylation of an allyl aminoalcohol. O-alkenylation followed by Claisen rearrangement under ligand-free conditions showed high selectivity, leading to the target compound. Subsequent intramolecular condensation completed the synthesis pathway.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Organic
Guang-Gao Fan, Bo-Wen Jiang, Wei Sang, Hua Cheng, Rui Zhang, Bao-Yi Yu, Ye Yuan, Cheng Chen, Francis Verpoort
Summary: A metal-free and solvent-free protocol was developed for the C-N coupling of heteroaryl halides and amines, yielding numerous heteroaryl amines or their hydrochlorides without the need for any external base. The basicity of amines and specific interactions derived from X-ray crystallography analysis played pivotal roles in the reactions. The protocol was scalable to gram scales and applicable to drug molecules, demonstrating its practical value for further applications.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Alpa Sharma, Harpreet Kour, Jaspreet Kour, Kamal, Sanghapal D. Sawant
Summary: A catalytic oxidative addition of sulfoximines to naphthoquinones via C-H functionalization has been achieved using an iron catalytic system. It shows good reactivity and high regioselectivity in the presence of visible light. This study provides an efficient protocol for obtaining (naphtho)quinone-sulfoximine hybrid analogs in moderate to good yields with a wide scope for substrates. The protocol has also been successfully applied to the modification of natural products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Dmitry A. A. Dulov, Tatiana V. V. Magdesieva
Summary: It has been demonstrated that inexpensive and readily available N,N'-diaryldihydrophenazines can effectively replace Ir(III)- and Ru(II)-based photocatalysts in the dual photoredox/Ni(II)C-N coupling of aryl halides with a wide range of anilines, as shown by 32 examples. This efficient and operationally simple approach to diarylamines can be scaled up using a flow apparatus.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Yuki Umakoshi, Yusuke Takemoto, Akira Tsubouchi, Viktor V. Zhdankin, Akira Yoshimura, Akio Saito
Summary: A transition metal iodine catalyst is used to synthesize oxazoles through C-C bond formation between unfunctionalized alkynes and arenes, resulting in the introduction of aryl groups into the side chain of the compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Zhi-Jun Jia, Gang Shan, Constantin G. Daniliuc, Andrey P. Antonchick, Herbert Waldmann
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Organic
Kiran Matcha, Andrey P. Antonchick
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Zhi-Jun Jia, Hiroshi Takayama, Yushi Futamura, Harumi Aono, Jonathan O. Bauer, Carsten Strohmann, Andrey P. Antonchick, Hiroyuki Osada, Herbert Waldmann
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Srimanta Manna, Andrey P. Antonchick
Article
Chemistry, Multidisciplinary
Houhua Li, Rajesh Gontla, Jana Flegel, Christian Merten, Slava Ziegler, Andrey P. Antonchick, Herbert Waldmann
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Organic
Mahesh Puthanyeedu, Vasiliki Polychronidou, Andrey P. Antonchick
Article
Chemistry, Organic
Saad Shaaban, Houhua Li, Christian Merten, Andrey P. Antonchick, Herbert Waldmann
Summary: The study reported a method for the catalytic enantioselective C-H functionalization for enantioenriched cyclopropylamines using a chiral RhJasCp complex. This method operates under mild conditions with high enantiocontrol, enabling access to cyclopropylamines with three contiguous stereocenters originating from the corresponding cyclopropenes.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Mahesh Puthanveedu, Vladislav Khamraev, Lukas Brieger, Carsten Strohmann, Andrey P. Antonchick
Summary: A transition-metal-free direct electrolytic C-H amination involving an electrochemically generated nitrenium ion intermediate has been developed. The electrosynthesis takes place in the absence of any organoiodine catalysts and is enabled by an in situ generated electrolyte. A novel, efficient intramolecular and intermolecular C-H amination has been demonstrated using a simple reaction setup.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Vasiliki Polychronidou, Anna Krupp, Carsten Strohmann, Andrey P. Antonchick
Summary: A metal-free protocol for the synthesis of substituted 1,6-dihydropyridines with quaternary stereogenic centers has been developed, demonstrating high functional group compatibility and broad scope. Modification of products allows for increased complexity and chemical diversity, with attempts at asymmetric synthesis shown.
Article
Chemistry, Medicinal
Fabian Wesseler, Daniel Riege, Mahesh Puthanveedu, Jonas Halver, Eva Mueller, Jessica Bertrand, Andrey P. Antonchick, Sonja Sievers, Herbert Waldmann, Dennis Schade
Summary: We report on the feasibility of using embryonic development in vitro to identify small-molecule cytokine mimetics and signaling activators. A target-agnostic high-throughput assay was used to probe BMP signaling during the patterning of embryonic stem cells. Through a chemical screen and hit validation, 2,3-disubstituted 4H-chromen-4-ones were identified as potent BMP potentiators with osteogenic efficacy. These findings provide novel chemical probes for (stem) cell biology, regenerative medicine, and basic research on the BMP pathway.
JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chunngai Hui, Lukas Brieger, Carsten Strohmann, Andrey P. Antonchick
Summary: This report presents a contractive synthesis of multisubstituted cyclobutanes from readily accessible pyrrolidines using iodonitrene chemistry. The stereospecific synthesis of cyclobutanes through a radical pathway mediated by a nitrogen extrusion process is described, resulting in the successful preparation of unprecedented unsymmetrical spirocyclobutanes, as well as a concise, formal synthesis of the cytotoxic natural product Piperarborenine B.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Chunngai Hui, Luke Craggs, Andrey P. Antonchick
Summary: This review provides an overview of the synthetic methods for ring contractions to form cyclopropanes, cyclobutanes, and cyclopentanes en route to structurally intriguing carbocycles.
CHEMICAL SOCIETY REVIEWS
(2022)
Review
Chemistry, Organic
Chunngai Hui, Andrey P. Antonchick
Summary: This study introduces a new reactive electrophilic aminating reagent, iodonitrene, which can transfer NH-group directly to nucleophilic atoms and has led to the development of new reactions. The application of iodonitrene has promising prospects, although there are current limitations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Saad Shaaban, Houhua Li, Felix Otte, Carsten Strohmann, Andrey P. Antonchick, Herbert Waldmann
Article
Chemistry, Multidisciplinary
Luis Bering, Laura D'Ottavio, Giedre Sirvinskaite, Andrey P. Antonchick
CHEMICAL COMMUNICATIONS
(2018)
