Article
Chemistry, Applied
Xiaoting Gu, Xiaoxiang Zhang, Wenhua Yu, Ke Sun, Wanxing Wei, Zhuan Zhang, Taoyuan Liang
Summary: This study presents a directing-group-free, three-component tandem C3-acylation/C5,6-H disulfenylation method for the position-selective functionalization of the poorly reactive benzenoid nucleus of indoles. The protocol demonstrates exceptional regio- and chemo-selectivity, broad substrate scope, good functional group tolerance, and mild reaction conditions. Importantly, this method offers great potential for the development of general site-selective functionalization at the benzenoid nucleus of indoles without the requirement for neighboring activating groups.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Rekha Thakur, Iqubal Singh, Kamaldeep Paul
Summary: In this study, direct C-H alkenylation of 1,8-naphthalimide using cyclic imide as a weak directing group and ruthenium catalyst was explored. The alkenyl group(s) were successfully introduced into the 1,8-naphthalimide skeleton at the inactive C2 and/or C7 positions. The aromatic ring of 1,8-naphthalimide was substituted with electron-withdrawing and electron-donating groups, and N-alkyl/aryl groups on cyclic imide were found compatible in these coupling reactions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jinwon Jeon, Changseok Lee, Inyoung Park, Sungwoo Hong
Summary: This article highlights the elegant and versatile approach of chelation-assisted C-H bond and alkene functionalization using bidentate directing groups, which overcomes regiocontrol issues. The focus is on two categories of results: regioselective alkene functionalization and asymmetric C-H functionalization using chiral bidentate directing groups. Additionally, density functional theory studies are discussed to elucidate the origin of regio- and stereoselectivity induced by bidentate directing groups.
Article
Chemistry, Multidisciplinary
Daniel Lee, Sean P. Ross, Xiao Xiao, Thomas R. Hoye
Summary: Polycyclic, highly fused, and highly conjugated aromatic organic compounds have been of interest to chemists since the discovery of naphthalene in 1821. In recent decades, these compounds have attracted increasing attention due to their structures, properties, and wide-ranging practical applications. The development of new methods and strategies for synthesizing polycyclic aromatic compounds with new structural motifs is important in order to create novel molecular topologies.
Article
Chemistry, Multidisciplinary
Hongyu Wang, Chen-Fei Liu, Robert T. Martin, Osvaldo Gutierrez, Ming Joo Koh
Summary: This study presents a new directing-group-free, nickel-catalysed strategy for the catalytic addition of carbogenic groups to unactivated and activated olefins with control of regioselectivity, achieving up to 93% yield and >98% site selectivity. The method can be extended to other types of reactions by switching reagents, and mechanistic and computational investigations provide insights into the regiochemical outcome of the reaction. The utility of the method is demonstrated through the concise syntheses of biologically active molecules, and the reported catalyst control principles are expected to advance efforts towards developing general site-selective alkene functionalizations.
Article
Chemistry, Multidisciplinary
Zhonglin Liu, Lucas J. Oxtoby, Mingyu Liu, Zi-Qi Li, Van T. Tran, Yang Gao, Keary M. Engle
Summary: The study reports a new method facilitated by a transient directing group for the vicinal fluorofunctionalization of alkenes, leading to the construction of vicinal stereocenters with excellent selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Editorial Material
Chemistry, Multidisciplinary
Rui Zhang, Guangbin Dong
Summary: In this issue of Chem, Morandi and coworkers describe an exciting reversible transfer hydroarylation reaction between ketones and unstrained arylated alcohols. The reaction involves a Rh-catalyzed beta-aryl elimination process, allowing for the transfer of an aryl group from the alcohol to the ketone substrate and providing a milder alternative to conventional Grignard and organolithium addition chemistry.
Review
Chemistry, Multidisciplinary
Liam S. Fitzgerald, Miriam L. O'Duill
Summary: This review discusses strategies for efficient removal of directing groups, focusing on the widely used N,N-bidentate directing group 8-aminoquinoline. The limitations of these strategies and alternative approaches for challenging substrates are also discussed. The aim is to provide a comprehensive guide for chemists in academia and industry to harness the synthetic power of directing groups and remove them from final products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sheuli Sasmal, Gaurav Prakash, Uttam Dutta, Ranjini Laskar, Goutam Kumar Lahiri, Debabrata Maiti
Summary: Site-selective C-H alkynylation of arenes is highly desirable for the synthesis of natural products, drug molecules, and materials. In this study, we developed a Rh(I)-catalyzed protocol for meta-C-H alkynylation, which broadens the scope of this transformation and allows for post-synthetic modifications.
Review
Chemistry, Multidisciplinary
Yingtao Wu, Chao Pi, Yangjie Wu, Xiuling Cui
Summary: Directing group migration has emerged as a practical strategy for transition-metal-catalysed direct C-H activation, leading to highly atom-economical processes and enabling the reusage of directing groups. Progress has been made in developing multitasking directing groups, with the focus on different types of migratable directing groups and their mechanisms, as well as synthetic applications.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Analytical
Changding Wang, Xiaohui Xu, Guoyu Qiu, Weichun Ye, Yumin Li, Richard A. Harris, Chaoyang Jiang
Summary: This study developed Ag nanosheets/ZnO nanoparticles hybrids with specific metal facets and additional charge transfer effect, established a calibration curve for estazolam, and achieved group-targeting screening of total concentrations of five BZDs.
ANALYTICAL CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Jayabrata Das, Wajid Ali, Debabrata Maiti
Summary: In this review, the development of C(sp3)-H activation is highlighted, including its origins, progression, and overcoming of limitations, to identify future research directions. The three main strategies for C(sp3)-H activation in aliphatic molecules are static directing group (DG) or template-assisted approach, transient DG (TDG) approach, and native functional group (NFG)-assisted approach. Each section provides a brief discussion on the evolution, functionalization type, advantages, and shortcomings of C(sp3)-H activation.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xu Ma, Zhitong Zheng, Yue Fu, Xijun Zhu, Peng Liu, Liming Zhang
Summary: This study introduces a strategy for the formation of 1,2-cis-glycosidic linkage using gold catalysis, achieving excellent yields and outstanding selectivities under mild conditions. This strategy is also successfully applied to the synthesis of oligosaccharides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Mingyu Liu, Juntao Sun, Tugce G. Erbay, Hui-Qi Ni, Raul Martin-Montero, Peng Liu, Keary M. Engle
Summary: This paper describes a palladium(II)-catalyzed C(alkenyl)-H alkenylation reaction enabled by a transient directing group strategy. The reaction takes advantage of reversible condensation between the substrate and a transient directing group to facilitate the coordination of the metal catalyst and subsequent activation of the C(alkenyl)-H bond. The reaction produces 1,3-dienes with high regio- and E/Z-selectivity and enables the synthesis of enantioenriched atropoisomeric 2-aryl-substituted 1,3-dienes that have seldom been studied before. The reaction mechanism and stereoinduction model were elucidated by density functional theory calculations and the alkenyl palladacycles were characterized by X-ray crystallography.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Jiao-li Ma, Xu-ming Zhou, Jia-lin Chen, Jie-xin Shi, Hui-cheng Cheng, Peng-hu Guo, Hong-bing Ji
Summary: Construction of a carbon-nitrogen bond is a common operation in nature and organic synthesis. Rhodium-catalyzed C-H amination with directing-group strategies improves the step economy and atom economy of the reaction, complying with green chemistry principles. The reactivity and selectivity of chelation-assisted rhodium-catalyzed C-H amination are discussed, along with the challenges and future prospects in this field.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Takashi Ikawa, Yuta Sumii, Shigeaki Masuda, Ding Wang, Yuto Emi, Akira Takagi, Shuji Akai
Article
Chemistry, Organic
Yumiko Suzuki, Naoto Iwata, Kohei Dobashi, Ryo Takashima, Sundaram Arulmozhiraja, Erika Ishitsubo, Naoya Matsuo, Hiroaki Tokiwa
Article
Biochemistry & Molecular Biology
Yurina Miyashita, Nobutaka Numoto, Sundaram Arulmozhiraja, Shogo Nakano, Naoya Matsuo, Kanade Shimizu, Osamu Shibahara, Michiko Fujihara, Hiroki Kakuta, Sohei Ito, Teikichi Ikura, Nobutoshi Ito, Hiroaki Tokiwa
Article
Chemistry, Multidisciplinary
Takashi Ikawa, Shigeaki Masuda, Shuji Akai
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Takashi Ikawa, JingKai Sun, Akira Takagi, Shuji Akai
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Correction
Chemistry, Organic
Takashi Ikawa, JingKai Sun, Akira Takagi, Shuji Akai
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Takashi Ikawa, Yuta Yamamoto, Akito Heguri, Yutaka Fukumoto, Tomonari Murakami, Akira Takagi, Yuto Masuda, Kenzo Yahata, Hiroshi Aoyama, Yasuteru Shigeta, Hiroaki Tokiwa, Shuji Akai
Summary: In recent years, it has been discovered that London dispersion interactions play an important role in controlling the regio- and stereo-selectivity of reactions. These interactions are dominant in selective catalysis, while repulsive steric interactions are predominant in noncatalytic reactions. A novel method utilizing London dispersion interactions has been developed for the synthesis of proximal biphenylenes, which have potential applications in ligands, catalysts, and medicines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Shuhei Hori, Sho Ishida, Go Itoh, Koji Sugiyama, Chiharu Yuki, Masahiro Egi, Kenzo Yahata, Takashi Ikawa, Shuji Akai
Summary: 4,5,6,7-Tetrahydroisobenzofurans, corresponding to the AC(D)E ring structure of viridin with required substituents on the A-ring, were synthesized via Diels-Alder adduct of a furan derivative and maleic anhydride with high regio- and stereoselectivities. Key steps in this synthesis included regioselective ring opening, stereoselective epoxidation, and AlMe3-mediated regioselective epoxide opening followed by stereoselective C-methylation.
Article
Chemistry, Multidisciplinary
Tsuyoshi Yamada, Akiko Fujii, Kwihwan Park, Chikara Furugen, Akira Takagi, Takashi Ikawa, Hironao Sajiki
Summary: An intramolecular cyclization reaction using alkynyl cyclic acetals as substrates and silver triflate or boron trifluoride etherate as catalysts has been developed for the synthesis of various phenanthrene derivatives. The reaction mechanism involves either alkyne activation or acetal activation pathways based on pi- or sigma-Lewis acidities, as suggested by the X-ray structure analysis and computational density functional theory study.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Organic
Naoki Oka, Tsuyoshi Yamada, Hironao Sajiki, Shuji Akai, Takashi Ikawa
Summary: A wide range of aryl boronic esters were synthesized and easily purified, showing higher yields in Suzuki-Miyaura couplings compared to aryl boronic acids or pinacol esters.
Article
Chemistry, Organic
Kwihwan Park, Shinichi Furusato, Chikara Furugen, Takashi Ikawa, Tsuyoshi Yamada, Hironao Sajiki
Summary: In this study, a solvent-free ruthenium-on-carbon-catalyzed hydrogenation reaction of CBDK was developed for the production of cis-CBDO, and the reaction mechanism for cis-selectivity was proposed based on density functional theory (DFT) calculations.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Satoshi Horino, Tomoya Nishio, Shinji Kawanishi, Shinya Oki, Koichi Nishihara, Takashi Ikawa, Kyohei Kanomata, Karla Wagner, Harald Groeger, Shuji Akai
Summary: In this study, a method for obtaining S enantiomers from secondary 3-(trialkylsilyl)propargyl alcohols was achieved by using a well-known R-selective Pseudomonas fluorescens lipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. Immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the dynamic kinetic resolution.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Kwihwan Park, Naoki Oka, Yoshinari Sawama, Takashi Ikawa, Tsuyoshi Yamada, Hironao Sajiki
Summary: We developed a platinum-catalyzed deuteration reaction using deuterium oxide as a deuterium source, which selectively deuterated tert-allylic alcohols with good deuterium content. The obtained deuterium-labeled allylic alcohols were further transformed into various deuterium-labeled building blocks without degradation of the original deuterium content.
ORGANIC CHEMISTRY FRONTIERS
(2022)
