Article
Chemistry, Multidisciplinary
Jingyi Wang, Xuzhong Shen, Xu Chen, Yinwei Bao, Jian He, Zhan Lu
Summary: In this study, cobalt-catalyzed enantioconvergent cross-coupling of alpha-bromoketones with aryl zinc reagents was achieved, leading to the synthesis of chiral ketones with alpha-tertiary stereogenic centers. Ligand modification was found to be critical for improving the reactivity and selectivity of this transformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Philipp Spiess, Saad Shaaban, Daniel Kaiser, Nuno Maulide
Summary: Umpolung is a term describing the reversal of innate polarity, which has become an important tool in synthetic organic chemistry. In this Account, the authors provide an overview of established methods and summarize their findings in the rapidly developing field of umpolung of carbonyl derivatives. They focus on the alpha-umpolung of amides enabled by electrophilic activation and the enolonium chemistry of ketones enabled by hypervalent iodine reagents. The authors discuss the challenges and achievements of these reactions, as well as mechanistic aspects. Rating: 8/10.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Xiangxiang Kong, Jing Ren, Jinlong Li, Yu Liu, Kaizhi Li
Summary: A novel copper-catalyzed cross-dehydrogenative-coupling (CDC) process has been developed for the straightforward synthesis of alpha-aryl-alpha-heteroaryl alpha-amino acid scaffolds using arylglycine derivatives and N-heteroarenes. This protocol demonstrates a wide substrate scope and good functional group compatibility by utilizing air as the sole oxidant. The reaction also allows for late-stage functionalization of arylglycines bearing natural compounds or drug motifs.
Article
Chemistry, Organic
Biplab Keshari Pandia, Chidambaram Gunanathan
Summary: The unprecedented manganese-catalyzed direct alpha-alkenylation of amides using alcohols was reported, providing alpha,beta-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies showed that the selective olefination is facilitated by metal-ligand cooperation, resulting in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Abhishek A. Kadam, Tanner L. Metz, Colton M. David, Mason T. Koeritz, Levi M. Stanley
Summary: In this study, a novel palladium-catalyzed reaction was disclosed using imides as acyl electrophiles to prepare a series of polycyclic compounds. The reaction achieved moderate to high yields of α,β-unsaturated ketones, which were readily transformed into polycyclic architectures via thermal hetero-Diels-Alder reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Le-Cheng Wang, Bo Chen, Xiao-Feng Wu
Summary: A novel cobalt-catalyzed carbonylative coupling of ethers with amines has been achieved, leading to the synthesis of biologically active compounds. This protocol presents the first example of direct carbonylative reaction of ethers, providing an important method for the construction of alpha-carbonylated ethers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Boya Feng, Guodong Zhang, Xu Feng, Yu Chen
Summary: A palladium-catalyzed decarbonylative methylation of aryl carboxylic acids using trimethylboroxine as the methylating reagent is described. The Pd(OAc)(2)/XantPhos system is compatible with a wide range of carboxylic acids and derivatives, including aroyl chloride/fluoride. The successful methylation of bioactive molecules and examples of orthogonal cross-couplings demonstrate the practicality of this method.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Ji-Wei Sang, Qiuhao Li, Chi Zhang, Yu Zhang, Jinxin Wang, Wei-Dong Zhang
Summary: A catalytic nickel-photoredox process for the direct amidation of aldehydes with nitroarenes was developed, where aldehydes and nitroarenes were activated by the photocatalytic cycle without the need for additional reductants or oxidants. This process facilitated the Ni-mediated cross-coupling of the C-N bond under mild conditions. A preliminary mechanistic study suggests that nitrobenzene is directly reduced to aniline as the nitrogen source.
Article
Chemistry, Organic
Jiamin Wu, Jinli Zhang, Yongjuan Jiao, Gongtao Deng, Yingmei Li, Zhengyu Zhang, Yaojia Jiang
Summary: A unique decarbonylation of an amino acid derivative catalytic system has been developed via palladium-catalyzed C-C bond and C-N bond dual activations. This approach provides a straightforward avenue for constructing diverse functionalized amide compounds in good to excellent yields. The proposed reaction pathway may involve C-C bond and C-N bond dual activations based on mechanistic studies.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Plant Sciences
Zhi-Yong Jiang, Jin-E Feng, Li-Kun Duan, Chun-Jiang Liu, Xiao-Fei Li, Chun-Qiu Huang, Sheng-Li Shi, Rui-Rui Wang, Ai-Xue Zuo, Hong-Ping He
Summary: Thirty-five tigliane diterpenoids and two ent- kaurane diterpenoids were isolated from Croton damayeshu leaves, and new tigliane diterpenoids were characterized. These compounds were tested for larvicidal, antifungal, and alpha-glucosidase inhibitory activities, and several showed promising results.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Multidisciplinary
Giuseppe Zuccarello, Suzanne M. Batiste, Hyungdo Cho, Gregory C. Fu
Summary: Due to increasing interest in the pharmaceutical industry, the synthesis of chiral alpha-aminoboronic derivatives has become an important challenge. In this study, we demonstrate the enantioselective synthesis of these derivatives using a chiral copper catalyst generated from commercially available components. Mechanistic studies were also conducted to optimize the process and provide insights into the reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jagannath Rana, Palaniyappan Nagarasu, Murugan Subaramanian, Akash Mondal, Vedichi Madhu, Ekambaram Balaraman
Summary: The general and efficient C(alpha)-alkylation of oxindoles with unactivated secondary alcohols as alkylating agents catalyzed by a newly developed NNN-Mn(II) complex demonstrates the importance of the NH moiety in the complex and M-L cooperation during the catalytic transformation.
Article
Chemistry, Multidisciplinary
Sergio Cuesta-Galisteo, Johannes Schorgenhumer, Xiaofeng Wei, Estibaliz Merino, Cristina Nevado
Summary: This study presents a nickel-catalyzed asymmetric reductive hydroarylation method for synthesizing enantioenriched alpha-arylbenzamides. By using a BIm ligand, diethoxymethylsilane, and aryl halides, aryl groups can be selectively introduced to the internal position of the olefin, creating a new stereogenic center alpha to the N atom with neutral reagents and mild reaction conditions. This provides a straightforward route to pharmacologically relevant motifs found in anticancer drugs, SARS-CoV PLpro inhibitors, and KCNQ channel openers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Christian D. -T. Nielsen, Filip G. Zivkovic, Franziska Schoenebeck
Summary: The study reported a synthetic method for N-trifluoromethyl alkynamides and found that this synthetic compound can serve as a platform to unlock access to other valuable derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Ayaka Ueda, Yusuke Aihara, Shinya Sato, Keiko Kano, Emi Mishiro-Sato, Hiroyuki Kitano, Ayato Sato, Kazuhiro J. Fujimoto, Takeshi Yanai, Kazuma Amaike, Toshinori Kinoshita, Kenichiro Itami
Summary: This study discovered 2,6-dihalopurines as a new inhibitor of stomatal opening and investigated its mechanism. Biological assays suggested that the pathway related to plasma membrane H+-ATPase phosphorylation may be involved. Through affinity-based pull down assay and molecular dynamics simulation, Leucine-rich repeat extensin proteins (LRXs), LRX3, LRX4, LRX5, and RALF were identified as target protein candidates for 2,6-dihalopurines. The mechanism of stomatal movement related to LRXs-RALF is an unexplored pathway, and further studies may uncover new signaling pathways and regulatory factors in stomatal movement.
ACS CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Ayaka Ueda, Kazuma Amaike, Yoko Shirotani, Hideto Ito, Robin Warstat, Jae-Hoon Choi, Hirokazu Kawagishi, Kenichiro Itami
Summary: Imidazole-4-carboxamide (ICA), a type of fairy chemical (FCs) causing fairy ring phenomena, exhibits plant growth inhibitory activity. FCs have the potential to be a new family of plant hormones as they are endogenous in all tested plant species and regulate plant growth. This study focuses on the synthesis of ICA derivatives and evaluation of their activity in rice. Surprisingly, several compounds show unexpected elongation activity in root and shoot growth.
CANADIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kou P. Kawahara, Hideto Ito, Kenichiro Itami
Summary: We have developed a sulfur-embedding annulative pi-extension (thia-APEX) reaction to efficiently construct a sulfur-embedding cationic hexagonal aromatic ring called thiopyrylium onto unfunctionalized aromatics in a one-step process. The key of the thia-APEX reaction lies in the utilization of S-imidated ortho-arenoyl arenethiols, enabling easy synthesis of diverse pi-extended thiopyryliums. The synthesized thiopyryliums exhibit various absorption and emission properties across the visible light to NIR region, depending on minor structural variations.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wataru Matsuoka, Kou P. Kawahara, Hideto Ito, David Sarlah, Kenichiro Itami
Summary: In this study, we successfully achieved a late-stage pi-extension of rubrene using dearomative annulative pi-extension (DAPEX), leading to the generation of rubrene derivatives with an extended aromatic core. These pi-extended rubrenes displayed a marked red shift in absorption and emission spectra, indicating the extension of the rubrene's aromatic pi-system both structurally and electronically. Furthermore, organic field-effect transistor devices using two-side pi-extended rubrene were fabricated, demonstrating the potential utility of these compounds in organic electronics with a comparable carrier mobility to rubrene thin-film transistors.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Nobushige Kai, Hideya Kono, Akiko Yagi, Kenichiro Itami
Summary: A novel structurally constrained nanobelt, methylene bridged [6]cyclo-2,6-naphthylene ([6]MCN), was synthesized via the nickel-mediated intramolecular aryl-aryl coupling of a triflated prism[6]arene. The structural and electronic properties of [6]MCN were characterized using NMR studies and photophysical measurements. In contrast to methylene-bridged [6]cycloparaphenylene, our previously synthesized benzene-based analogue, [6]MCN exhibited low strain energy (77.4 kcalmiddotmol(-1)) and bright fluorescence (Phi = 0.20).
Article
Chemistry, Medicinal
Aya Ogata, Takashi Yamada, Saori Hattori, Hiroshi Ikenuma, Junichiro Abe, Mari Tada, Masanori Ichise, Masaaki Suzuki, Kengo Ito, Takashi Kato, Kazuma Amaike, Tsuyoshi Hirota, Akiyoshi Kakita, Kenichiro Itami, Yasuyuki Kimura
Summary: Positron emission tomography (PET) is a powerful imaging tool for early detection of Alzheimer's disease (AD) that has been developed to target beta-amyloid and tau protein aggregates. This study focuses on the development of a new PET ligand targeting protein kinase CK2, which is known to be altered in AD brains.
BIOORGANIC & MEDICINAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Hideya Kono, Yuanming Li, Guglielmo Monaco, Riccardo Zanasi, Francesco F. Summa, Lawrence T. Scott, Akiko Yagi, Kenichiro Itami
Summary: Cycloparaphenylenes (CPPs) and carbon nanobelts (CNBs) are cyclic molecular nanocarbons with unique properties derived from rigid, strained, and cyclic p-conjugated systems. The synthesis of various sizes of CPPs and CNBs has allowed for the investigation of their size-dependent properties and use in various applications. The synthesis, size-dependent properties, and paratropic belt currents of methylene-bridged [n]cycloparaphenylenes ([n]MCPP, n = 6, 8, 10) were reported and studied.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kanna Fujishiro, Yuta Morinaka, Yohei Ono, Tsuyoshi Tanaka, Lawrence T. Scott, Hideto Ito, Kenichiro Itami
Summary: In this study, a lithium(0)-mediated mechanochemical anionic cyclodehydrogenation reaction was developed for the first time. The reaction could be easily performed using a conventional and easy-to-handle lithium(0) wire at room temperature, even under air, and achieved high yields in a short time. The study also comprehensively investigated the applicability and practicality of the protocol, as well as limitations, through computational studies and nuclear magnetic resonance analysis. Furthermore, novel nanographenes, including quinterrylene, were successfully synthesized using this method.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Takaku Yoshihara, Hiroki Shudo, Akiko Yagi, Kenichiro Itami
Summary: Peripheral structural modifications of arenes have a significant impact on their optoelectronic properties, molecular assembly, and stability. Annulation with an adamantane scaffold is a simple yet powerful modification strategy that leads to unique effects, such as high solubility and enhanced conjugation. The oxidation of adamantane-annulated perylenes produces cationic species with extended emission in the near-infrared region, potentially contributing to the development of groundbreaking pi-materials and novel nanocarbon materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Yusuke Aihara, Bumpei Maeda, Kanna Goto, Koji Takahashi, Mika Nomoto, Shigeo Toh, Wenxiu Ye, Yosuke Toda, Mami Uchida, Eri Asai, Yasuomi Tada, Kenichiro Itami, Ayato Sato, Kei Murakami, Toshinori Kinoshita
Summary: The authors identify BITC as a stomatal opening inhibitor that suppresses PM H+-ATPase phosphorylation. They develop BITC derivatives with higher inhibitory activity that increase drought tolerance in plants.
NATURE COMMUNICATIONS
(2023)
Article
Plant Sciences
Yuki Nakashima, Yuka Kobayashi, Mizuki Murao, Rika Kato, Hitoshi Endo, Asuka Higo, Rie Iwasaki, Mikiko Kojima, Yumiko Takebayashi, Ayato Sato, Mika Nomoto, Hitoshi Sakakibara, Yasuomi Tada, Kenichiro Itami, Seisuke Kimura, Shinya Hagihara, Keiko U. U. Torii, Naoyuki Uchida
Summary: A compound called PLU has been discovered to induce the formation of pluripotent callus in plants without the need for external hormone application. The PLU-induced callus expresses marker genes associated with pluripotency acquisition. This study provides a new approach to manipulate and investigate the induction of plant pluripotency.
FRONTIERS IN PLANT SCIENCE
(2023)
Article
Chemistry, Organic
Jaehyun Jung, Takumi Kinoshita, Yuta Makihara, Yota Sakakibara, Kazuma Amaike, Kei Murakami, Kenichiro Itami
Summary: In this study, a decarboxylative aminomethylation of aryl bromides with N-protected glycine under nickel/photoredox-catalyzed conditions was reported. The resulting products can be easily deprotected under acidic conditions to give primary benzylamines.
Review
Chemistry, Organic
Hideto Ito, Kou P. Kawahara, Kenichiro Itami
Summary: Heteroatom-embedded polycyclic aromatic compounds (hetero-PACs) are important in various research fields, and efficient preparation is crucial. This review describes the reactions transforming unfunctionalized aromatic compounds into hetero-PACs using appropriate heteroatom-containing aromatic compounds.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Kou P. Kawahara, Hideto Ito, Kenichiro Itami
Summary: This paper describes the synthesis of pi-extended thianthrene derivatives from unfunctionalized aromatics using thia-APEX reactions. The reaction involves the fusion of new benzodithiine arms to the aromatic substrates in one step, resulting in the formation of pi-extended thianthrenes with yields ranging from 21% to 87%. The reaction requires equimolar amounts of the aromatic substrates and S-diimidated 1,2-arenedithiols, along with a catalytic amount of TfOH, and the synthesized pi-extended thianthrenes were characterized for their solid state packing structures and photophysical properties.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Medicinal
Fumito Takada, Takahito Kasahara, Kentaro Otake, Takamitsu Maru, Masanori Miwa, Kei Muto, Minoru Sasaki, Yoshihiko Hirozane, Masato Yoshikawa, Junichiro Yamaguchi
Summary: This study reports the discovery of two compounds, TKD 150 and TKD152, that promote the aggregation of aSN. Compared to a previously reported proaggregator, PAS6, these two compounds have a stronger proaggregation effect and can shorten the inherent lag time of the RT-QuIC assay, potentially enabling wider use in the clinical diagnosis of alpha-synucleinopathy-related diseases.
ACS MEDICINAL CHEMISTRY LETTERS
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
