Article
Chemistry, Applied
Fei Zhao, Jing Chen, Jin Qiao, Yangbin Lu, Xiaoning Zhang, Hui Mao, Shiyao Lu, Xin Gong, Siyu Liu, Xiaowei Wu, Long Dai
Summary: This study achieved the synthesis of functionalized 1H-imidazo[1,5-a]indol-3(2H)-ones by utilizing electron-deficient alkynes as unconventional C-1 synthons in a redox-neutral rhodium(III)-catalyzed [4+1] annulation. The process exhibited high chemo- and regioselectivity, broad substrate scope, good tolerance of functional groups, moderate to high yields, and mild redox-neutral conditions, providing a robust method to access valuable 1H-imidazo[1,5-a]indol-3(2H)-ones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Jiajie Li, Xin Xu, Zhenli Luo, Zhen Yao, Ji Yang, Xin Zhang, Lijin Xu, Peng Wang, Qian Shi
Summary: Cp*Rh(III)-catalyzed regioselective C-H annulation and alkenylation of 2-pyridones with terminal alkynes has been developed, providing efficient access to diversified compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Ping Zhang, Wenju Chang, Hongyun Jiao, Yanshang Kang, Wenxuan Zhao, Peipei Cui, Yong Liang, Wei-Yin Sun, Yi Lu
Summary: The study established a successful electron-deficient catalyzed annulation of N-pentafluorophenylbenzamides with internal alkynes, aided by Lewis acid silver salt, exhibiting a broad tolerance for different substituents on aromatic rings or alkyl-substituted alkynes in the catalytic system.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Biplab Gope, Anupam Mishra, Satish K. Awasthi
Summary: The catalysis of directed C-H activation by transition metals is an important method in synthetic organic chemistry, allowing for the efficient synthesis of natural products, organic materials, and organic building blocks. Indole is an important target in organic chemistry, with applications in drug discovery and material development. By studying the rhodium-catalyzed C-H activation, researchers can access biologically active indole derivatives, opening up new possibilities for drug development and chemical biology research.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Qing-Feng Xu-Xu, Yuji Nishii, Yuta Uetake, Hidehiro Sakurai, Masahiro Miura
Summary: A rhodium-catalyzed direct selenium annulation using stable elemental selenium was introduced in this manuscript, leading to the successful synthesis of a series of isoselenazolones. A new selenation mechanism involving a highly electrophilic Se(IV) species as the reactive selenium donor was proposed and further verified by computational study.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Alfredo Pereira, Camilo Albornoz, Oleksandra S. Trofymchuk
Summary: This study presents a data-driven approach to analyze reactions catalyzed using [Cp*Co(CO)I-2]. By analyzing different parameters, the screening process in the laboratory is accelerated to yield favorable combinations. The research also demonstrates the effects of reaction conditions and directing groups on the reaction performance.
Article
Chemistry, Multidisciplinary
Anirudra Paul, Jae Hyun Kim, Scott D. Daniel, Daniel Seidel
Summary: Despite efforts by practitioners, direct alpha-C-H bond functionalization of unprotected alicyclic amines is rare. A new method utilizing N-lithiated alicyclic amines has been developed, providing a convenient approach to achieve functionalization reactions under mild conditions. This method offers a new pathway for the synthesis of beta-amino ketones with regioselective alpha'-alkylation, and potential for one-pot synthesis of polycyclic dihydroquinolones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Yao Yu, Yang Wang, Bo Li, Yuqiang Tan, Huan Zhao, Zheyu Li, Chunran Zhang, Wenbo Ma
Summary: This article presents a convenient and effective method of ruthenium-catalyzed C-H/N-H annulations using vinylene carbonate as an oxidizing acetylene surrogate. The method is scalable and compatible with a wide range of functional groups, offering a economical approach to indole synthesis. Preliminary mechanistic studies support a reversible, acetate-assisted C-H ruthenation, followed by olefin insertion.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Lingheng Kong, Xi Han, Haohua Chen, Huaming Sun, Yu Lan, Xingwei Li
Summary: The regioselective coupling of NH indoles with diazo compounds using dimeric Rh(II) complexes as catalysts demonstrates selectivity towards C(6) or C(7) positions depending on the structure of the indoles. Mechanistic studies reveal that hydrogen-bonding directing effect plays a crucial role in determining the regioselectivity, with C-C bond formation proceeding through Friedel-Crafts-type attack. This work highlights the challenges and opportunities in controlling regioselectivity in reactions involving arene C-H bonds.
Article
Chemistry, Organic
Demao Chen, Changfeng Wan, Yunyun Liu, Jie-Ping Wan
Summary: A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been developed via the reactions of enaminones, hydrazine hydrochloride, and internal alkynes using Rh catalysis. The cascade reactions demonstrate the remarkable high-order bond functionalization, involving the transformation of aryl C-H, ketone C=O, and alkenyl C-N bonds in the enaminones. This study highlights the individual advantage of enaminones in the design of novel and efficient synthetic methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Suho Kim, Su Bin Choi, Ju Young Kang, Won An, Suk Hun Lee, Harin Oh, Prithwish Ghosh, Neeraj Kumar Mishra, In Su Kim
Summary: The Rh(III)-catalyzed C-H annulation reactions provide a rapid access to indazolocinnolines and phthalazinocinnolines, which are important assets for developing novel bioactive compounds. Intriguingly, a vinylene carbonate acts as a vinyl transfer agent enabling the [4+2] annulation reaction, characterized by simplicity, mild reaction conditions, and broad functional group tolerance.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Juan Diego Pizarro, Lucia Moran-Gonzalez, Ivan Gonzalez-Fernandez, Feliu Maseras, Manuel R. Fructos, Pedro J. Perez
Summary: Copper catalysts containing ADAP ligand selectively functionalize unprotected indoles at the C3-H position through carbene transfer, without altering the N-H bond. Mechanistic studies, including DFT calculations, propose two competitive pathways that do not involve the formation of cyclopropane intermediates, contrasting with previous reports.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Shuaishuai Song, Yunfei Lai, Zekun Tuo, Jianming Zhong, Wang Zhou
Summary: A rhodium(III)-catalyzed oxidative cyclization of chalcones with internal alkynes is reported, resulting in the formation of biologically important 3,3-disubstituted 1-indanones and reusable aromatic aldehydes. This transformation exhibits a unique (4+1) reaction mode, excellent regioselectivity, broad substrate scope, ability to construct quaternary carbon centers, and scalability. Steric hindrance from the substrate and ligand likely controls the chemoselectivity of this carbocyclization. Importantly, this discovery enables a practical two-step protocol to switch the overall reaction from a (3+2) to a (4+1) annulation of acetophenones with internal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: This study describes an efficient and regioselective synthesis of isoquinolones by [4 + 2]-annulation of N-chlorobenzamides with vinyl acetate in the presence of CoCp*(III) catalyst. The annulation reaction was further diversified by using vinyl ketones, leading to the preparation of biologically valuable isoquinolone derivatives in good yields. Additionally, mechanistic investigations including deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: An efficient and straightforward strategy for the synthesis of isoquinolones through [4 + 2]-annulation was described. Through utilizing N-chlorobenzamides and vinyl acetate, isoquinolone derivatives were prepared in good yields with the presence of CoCp*(III) catalyst in a regioselective manner. Furthermore, the annulation reaction was diversified by using vinyl ketones. Mechanistic investigations such as deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Takanori Matsuda, Takeshi Matsumoto, Akira Murakami
Article
Chemistry, Organic
Takanori Matsuda, Kentaro Yamanaka, Yuki Tabata, Takahiro Shiomi
TETRAHEDRON LETTERS
(2018)
Article
Chemistry, Organic
Takanori Matsuda, Hirotaka Ito
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Takanori Matsuda, Shinya Abe, Hirotaka Ito, Tomoya Tsuboi, Haruki Kirikae, Masahiro Murakami
Article
Chemistry, Organic
Takanori Matsuda, Takashi Izutsu, Masaru Hashimoto
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Hirotsugu Suzuki, Yumeng Liao, Yuya Kawai, Takanori Matsuda
Summary: The rhodium-catalyzed C(sp(2))-H ethoxycarbonylation reaction of indoles and arylpyridines using diethyl dicarbonate was developed. This catalytic process features an additive-free reaction with only ethanol and CO2 produced as byproducts, providing a CO-free and operationally simple protocol. The introduced ethoxycarbonyl group can be easily transformed into other ester and amide functionalities in a single step.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hirotsugu Suzuki, Kenji Yoneoka, Sora Kondo, Takanori Matsuda
Summary: The first enantioselective reductive aldol reaction of unprotected alpha,beta-unsaturated carboxylic acids has been developed using a copper/bisphosphine catalyst. This reaction involves the in situ protection and activation of the carboxylic acid using a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to produce beta-hydroxy carboxylic acid with excellent enantioselectivity (up to 99% ee). The gram-scale reaction with low catalyst loading and the derivatization of the beta-hydroxy carboxylic acids highlight the practicality of this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Hirotsugu Suzuki, Fumito Sasamori, Takanori Matsuda
Summary: In this study, we developed a rhodium-catalyzed alkoxylcarbonylation/acylation method using anhydrides as the carbonyl source to synthesize C7-carbonylated indolines. This catalytic process is additive- and CO-free, and it successfully achieves the C-H acylation of indolines, leading to the formation of alpha-branched ketones that were difficult to prepare using previously reported analogous catalytic reactions.
Article
Chemistry, Organic
Hirotsugu Suzuki, Yosuke Takemura, Takanori Matsuda
Summary: We have developed a novel approach to synthesize indoloindolone through a rhodium-catalyzed intramolecular acylation of 2-(indol-1-yl)benzoic acids. This reaction proceeds by the in situ formation of a mixed anhydride under redox-neutral reaction conditions. Preliminary mechanistic studies revealed that the in situ formed mixed anhydride participates in the C-H activation step facilitated by a RhI catalyst. The usefulness of this reaction was demonstrated through a large-scale reaction.
Article
Chemistry, Organic
Hirotsugu Suzuki, Yuya Kawai, Yosuke Takemura, Takanori Matsuda
Summary: We developed a new catalytic system for the decarbonylative C(sp(2))-H alkylation of indolines. This method allows for the use of cheap, abundant, and non-toxic alkyl carboxylic acids and their anhydrides as an alkyl source, introducing a primary alkyl chain that was not possible with previous methods.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Hirotsugu Suzuki, Takahiro Shiomi, Kenji Yoneoka, Takanori Matsuda
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Organic
Takanori Matsuda, Souta Oyama
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Organic
Takanori Matsuda, Naoto Yonekubo
ORGANIC & BIOMOLECULAR CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Takanori Matsuda, Keisuke Fukuhara, Naoto Yonekubo, Souta Oyama
Article
Chemistry, Multidisciplinary
Takanori Matsuda, Yuki Tabata, Hirotsugu Suzuki
NEW JOURNAL OF CHEMISTRY
(2018)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
