Article
Chemistry, Organic
Fei Li, Weikang Xiong, Geyang Song, Yonggang Yan, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A general and efficient photochemical C-N coupling method for (hetero)aryl chlorides with hydrazides is presented. The reaction is catalyzed by a Ni(II)-bipyridine complex and does not require an external photosensitizer, making it highly practical. This method demonstrates a wide substrate scope (54 examples) and excellent functional group tolerance, and has been successfully applied to the synthesis of rizatriptan.
Article
Chemistry, Multidisciplinary
Yunhui Feng, Hang Luo, Fangnian Yu, Qian Liao, Luqing Lin
Summary: Here, we present a visible-light-promoted single nickel catalysis for achieving various C-N couplings of aryl chlorides/bromides and diverse N-nucleophiles using sodium iodide as the activator. The single nickel catalyst plays a dual role in halogen exchange and C-N coupling, which are crucial for obtaining the desired coupling products. This catalytic process eliminates the need for an exogenous photocatalyst and offers a sustainable and efficient approach for mild C-N coupling. Experimental studies, along with UV-vis and NMR analyses, demonstrate that the halogen exchange between both Ni-II and Ni-III-halide complexes and the iodide anion is a significant process in the formation of coupling products.
Article
Chemistry, Multidisciplinary
Gang Li, Liu Yang, Jian-Jun Liu, Wei Zhang, Rui Cao, Chao Wang, Zunting Zhang, Jianliang Xiao, Dong Xue
Summary: This study demonstrates a photochemical C-N coupling of aryl halides with nitroarenes for the first time, catalyzed by a Ni-II complex in the absence of any external photosensitizer. The method provides a step-economic extension to the widely used Buchwald-Hartwig C-N coupling reaction and tolerates coupling partners with steric-congestion and functional groups sensitive to bases and nucleophiles. Mechanistic studies suggest the reaction proceeds via the addition of an aryl radical, generated from a Ni-I/Ni-III cycle, to a nitrosoarene intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
He Liu, Jian Wu, Yuxuan Jin, Xuebing Leng, Qilong Shen
Summary: By studying the copper-mediated trifluoromethylation reaction, more reactive intermediates [CuCF3] and [(DMF)CuCF3] were discovered. A general mechanistic map for CuI-promoted trifluoromethylation reaction was proposed, leading to the development of a new trifluoromethylation method based on this mechanistic understanding.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Jing Li, Xiaoyu Wang, Zhanwei Wang, Yian Shi
Summary: A novel Cu-promoted C-N coupling reaction between boron esters and di-tert-butyldiaziridinone is described, allowing for the efficient synthesis of a wide variety of aryl ureas under mild conditions with up to a 92% yield.
Article
Chemistry, Physical
Angela Burhenn, Roberta Bavaro, Viktoria H. Gessner
Summary: In this study, a series of chloro- and polyhalogenated compounds, including polychlorinated biphenyls (PBCs) extracted from construction dust, were successfully dehalogenated under mild reaction conditions using palladium complexes with ylide-substituted phosphines (YPhos) as ligands. Ethanol was used as the hydride source in the reaction, and site-selective deuterations could be achieved by switching to deuteroethanol.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Cheng-Yu Long, Hao Chen, Cheng Ma, Bo-Wei Zhao, Shen-Huan Li, Yue Cui, Xinge Yang, Shao-Fei Ni, Xue-Qiang Wang
Summary: A Ni-catalyzed protecting-group-free C-C coupling protocol has been developed for the efficient synthesis of 2,2'-biphenol derivatives. This newly developed strategy demonstrates remarkable chemoselectivity control ability, wide substrate scope, and excellent functional group tolerance.
Article
Chemistry, Organic
Chuntao Zhong, Mengna Liu, Xianchao Qiu, Hao Wei, Benqiang Cui, Yanhui Shi, Changsheng Cao
Summary: A nickel-catalyzed cross-coupling reaction between aryl methyl sulfides and aryl bromides has been developed to efficiently access biaryls. The method has a wide scope of substrates and is scalable, with commercially available aryl bromides being used without the need for preparation of organometallic reagents. This reaction has high application value.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Dan Li, Li Wei, Wenfang Xiong, Huanfeng Jiang, Chaorong Qi
Summary: A palladium-catalyzed reductive formylation of aryl iodides with carbon dioxide as the carbonyl source was achieved using Pd(PCy3)2Cl2 and di-2-pyridyl ketone as the catalyst and phenylsilane as the reductive reagent under mild reaction conditions. The reaction provided a variety of aromatic aldehydes in moderate to excellent yields and exhibited good substrate scope, functional group tolerance, and easy operation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Pablo Gomez-Orellana, Agusti Lledos, Gregori Ujaque
Summary: The Buchwald-Hartwig amination of arylhalides with the Pd-Josiphos complex using ammonia as a reactant is a useful process for primary amine synthesis. Density-functional theory calculations were used to examine the reaction mechanism, revealing the importance of the chelate phosphine ligand and base in the process. The study allowed for the proposal of a complete reaction mechanism for the Pd-catalyzed C-N coupling reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hardeep Singh, Alyson MacKay, Nooshin Sheibany, Fei Chen, Maelle Mosser, Pierre-Etienne Rouet, Frederic Rousseau, Mohammad S. Askari, Xavier Ottenwaelder
Summary: Primary hydroxylamines, RNHOH, easily decompose in the presence of transition metal ions, but this reactivity can be prevented by ligand design with intramolecular hydrogen bonds. Six metal complexes with intact NHOH groups were synthesized and crystallographically characterized, showing that Cu-hydroxylamine complexes can catalyze the aerobic oxidation of benzylic alcohols.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Tishyasoumya Bera, Bandana Singh, Vincent Gandon, Jaideep Saha
Summary: This study reveals a S-N'-type intramolecular aromatic substitution reaction that forms oxindoles by activating alpha-aryl-alpha-chlorohydroxamate. The investigation highlights the crucial role of HFIP in the transformation and suggests the operative pathway is a non-pericyclic nucleophilic amination.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Tzu-Lun Liu, Meng-Li Jhou, Cheng-En Hsieh, Chia-Jung Lin, Hsiu-Hui Su, Chih-Ming Chou
Summary: This study presents a protocol for the preparation of functionalized N-allyl-N-aryl sulfonamides via palladium-catalyzed intramolecular decarboxylative N-allylation reaction, showing good regioselectivity. Additionally, transformation of N-allyl-N-aryl sulfonamide into 4-aryl-1,2,3,4-tetrahydroquinoline and nitrogen-containing beta-hydroxysulfide bioactives has been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Priyanka Yadav, Pradeep Kumar
Summary: The present study investigates the role of the external electric field in enhancing the C-N cross-coupling reaction between 2-chlorobenzoic acid and propylamine by calculating reaction rates and energy barriers. The findings suggest that the reaction can proceed without a barrier by choosing the appropriate direction of the electric field, resulting in a significantly increased reaction rate in the presence of an EEF. The efficiency of the electric field is also found to depend on the dipole moment of the reactants, indicating the general applicability of the results to various C-N cross-coupling reactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Organic
Richa Sharma, Sandeep Chaudhary
Summary: A new method of direct cyanation of N-aryl-(1H/2H)-indazoles via aerobic oxidative C(sp2)-H bond activation has been developed, which shows positional switch by including or excluding AcOH additive, resulting in good to excellent yields with high functional group tolerance. The use of molecular oxygen as a clean and safe oxidant allows for further transformation of the synthesized cyanated product into various other functional groups, showing potential applications in synthetic biology and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tatsuki Okumi, Atsunori Mori, Kentaro Okano
Summary: A regiocontrolled halogen dance reaction of 2,5-dibromopyrroles is reported using an N,N-dimethylsulfamoyl group to facilitate the interconversion of 2,3- and 2,4-dibromopyrrolyllithiums. This method was successfully applied to the formal synthesis of atorvastatin.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yushin Shibuya, Koki Susami, Hiroyuki Fukuoka, Seiha Yamaoka, Kentaro Okano, Atsunori Mori
Summary: Chiraphos acts as a highly effective ligand for nickel catalysts in cross-coupling polymerization reactions. The efficient nickel(II) catalyst promotes the cross-coupling polymerization of 2,5-differently substituted 1,4-dihalobenzene, particularly with a sterically congested substituent at the side chain, resulting in the formation of poly(1,4-phenylene). This catalyst exhibits high activity and enables control over the molecular weight and degree of polymerization.
Article
Chemistry, Applied
Masatoshi Yamada, Kazuki Azuma, Iori Takizawa, Yuki Ejima, Mitsuhisa Yamano, Kimio Satoh, Takayuki Doi, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: A scalable asymmetric total synthesis of (-)-emetine, an important component in emetics, has been achieved. The synthesis involved 13 steps of highly efficient chemical reactions, including catalytic asymmetric allylation and industrial deoxygenation, eliminating the need for chromatographic purification. A high yield of (-)-emetine center dot 2HCl (12%) with over 93.2% HPLC purity was obtained, and the synthesis can be easily scaled up for larger production and currently used in natural ipecac syrup for clinical application.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Materials Science, Multidisciplinary
Sonoka Yamamoto, Ryutaro Yamashita, Chihiro Kubota, Kentaro Okano, Masatoshi Kitamura, Masahiro Funahashi, Syu-Cheng Ye, Yung-Tin Pan, Masaki Horie, Takuji Shintani, Hironori Murata, Hideto Matsuyama, Atsunori Mori
Summary: A thiophene-thiophene block copolymer with hydrophilic and hydrophobic side chains was synthesized. The block copolymer exhibited cylindrical microphase separation and the hydrophilic domain penetrated perpendicular to the substrate. The conductive properties of the thin film changed depending on its orientation to the substrate, with parallel orientation being conductive and perpendicular orientation being insulative. Electrochemical analysis showed that lithium ions transferred through the cylindrical domain composed of benzene sulfonic acid side chains.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Hirofumi Ueda, Soichiro Sato, Kenta Noda, Hiroyuki Hakamata, Eunsang Kwon, Nagao Kobayashi, Hidetoshi Tokuyama
Summary: A biomimetic oxidative dimerization method for tryptophan derivatives was developed using oxygen as a bulk oxidant in aqueous media catalyzed by an iron octacarboxy phthalocyanine complex. The highly active iron catalyst enables aerobic enzyme-mimetic oxidation in a flask. This method provides a facile access to a broad range of dimerized peptides with unique scaffold, which can be used as a powerful tool for creating new small- and medium-sized molecules as drug candidates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama, M. Iyag
Summary: This study conducted synthetic studies on a dimeric indole alkaloid, cimicidu-phytine, by modifying the synthesis of (+)-haplophytine. The key aspects of this synthesis included the chemoselective deallylation of an N,O-diallyl derivative of a hydroxy aniline and the copper sulfate-mediated oxidative lactonization via oxidation of the amino moiety. A highly convergent strategy successfully synthesized the originally proposed cimiciduphytine, but it proved to be unstable under air and underwent cyclization to generate a bridged derivative.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Organic
Kentaro Okano, Yuya Okui, Atsunori Mori
Summary: A formal synthesis of dictyodendrin B was achieved by regiocontrolled functionalization of the alpha,beta-dibromopyrrole derivative, followed by reductive cyclization and further chemical transformation. The synthesis involved the construction of the characteristic tetracyclic pyrrolo[2,3c]carbazole skeleton and manipulation of the ester moiety.
Article
Chemistry, Organic
Yuxuan Feng, Taro Yukioka, Mei Matsuyama, Atsunori Mori, Kentaro Okano
Summary: A method for the regioselective functionalization of haloarenes through deprotonative lithiation is described. The haloaryllithiums generated were trapped with a zinc chloride diamine complex in a batch reactor, resulting in the formation of organozinc species without aryne formation. These species reacted with electrophiles to yield the corresponding products in yields of 38-98%. The method was successfully applied to the gram-scale, five-step total synthesis of carbazomycin A with an overall yield of 33%.
Article
Chemistry, Organic
Masahiro Hosoya, Atsunori Mori, Kentaro Okano
Summary: The regioselectivity for deprotonation of a pyridylthiophene can be controlled by changing the reaction conditions. In addition, the in situ transmetalation and halogen dance on the corresponding organometallic species can be controlled by additives, reaction temperature, and the above reaction conditions. As a result, this method enables the synthesis of four iodinated constitutional isomers from a single starting material, 2-(5-bromo-2-thienyl)pyridine.
Article
Chemistry, Organic
Seiha Yamaoka, Hiroyuki Fukuoka, Naoki Noda, Kentaro Okano, Masaki Horie, Atsunori Mori
Summary: A nickel thiocyanate complex was synthesized and used as a catalyst for various polymerization reactions and coupling reactions. The polymerization of 1,4-dihalobenzenes and 2-halo-3-hexylthiophenes resulted in the formation of poly-1,4-phenylenes and poly(3-hexylthiophene-2,5-diyl), respectively. The complex also catalyzed Suzuki-Miyaura couplings and Buchwald-Hartwig aminations, leading to the formation of biaryls and arylamines.
Article
Chemistry, Multidisciplinary
Kosuke Okada, Ken-ichi Ojima, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: The synthesis of (+)-pleiocarpamine, (+)-voacalgine A and (+)-bipleiophylline was achieved in this study. The 10-step synthesis of (+)-pleiocarpamine features the construction of stereochemistry at the C16 position by radical cyclization and the synthesis of the highly strained cage-like structure via Pd-catalyzed intramolecular aromatic C-H functionalization. By modifying the biomimetic aerobic oxidative coupling of tryptophane derivatives catalyzed by FePc(CO2H)(8), the oxidative coupling of (+)-pleiocarpamine with pyrocatechuic acid produced (+)-voacalgine A. The total synthesis of (+)-bipleiophylline was completed by the second coupling of (+)-voacalgine A with (+)-pleiocarpamine or the one-pot couplings of 2 equiv of (+)-pleiocarpamine with pyrocatechuic acid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Kengo Inoue, Atsunori Mori, Kentaro Okano
Summary: A two-step halogen transfer reaction of bromoarenes was reported. Bromoaryllithiums generated through deprotonative lithiation were converted into organozinc species by in situ zincation, followed by bromination to produce bromoarenes. It was also discovered that the bromo group could undergo regioselective translocation in the presence of ethylmagnesium chloride.
Article
Chemistry, Physical
Kohei Hosokawa, Kohei Tabuchi, Yuki Nakanishi, Kentaro Okano, Masaki Horie, Atsunori Mori
Summary: Multiple ring-closing metathesis of oligomeric bithiophene produced a vine-shaped oligomer with molecular asymmetry. Stereochemical studies revealed that the dimeric meso and racemic mixture converted to a meso-enriched product in the solid state, while the obtained meso compound reverted back to the meso and racemic mixture upon heating in chloroform solution. Heating the meso isomer in the solid state did not lead to isomerization.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Article
Chemistry, Organic
Kengo Inoue, Atsunori Mori, Kentaro Okano
Summary: A two-step halogen transfer method for bromoarenes was reported. By utilizing deprotonative lithiation and in situ zincation, organozinc species were generated and then subjected to bromination to obtain di-, tri-, and tetrabromoarenes with high yields. Regioselective bromine-magnesium exchange followed by electrophilic trapping resulted in benzene, pyridine, quinoline, pyrimidine, and thiazole derivatives with bromo group translocation.
Article
Chemistry, Organic
Yuko Wakahara, Takahiro Noro, Juri Sakata, Hirofumi Ueda, Hidetoshi Tokuyama
Summary: This study investigates the construction of tetrahydroquinolines with a spirocyclic structure at the 4-position. A five-step sequence was developed, including the synthesis of benzocyclopentanone oxime, followed by the addition of aryl Grignard Reagent, intramolecular Friedel-Crafts acylation, condensation with hydroxylamine, and reductive ring expansion reaction. The method was successfully used to construct various tetrahydroquinolines with spirocyclic rings of different sizes and adamantane and indane structures at the 4-position.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
