Article
Chemistry, Organic
Kailas V. Preeti, Kailas V. Kallurkar, Prathama S. Mainkar, Raju Adepu, Srivari Chandrasekhar
Summary: A concise route for the synthesis of dihydrobenzo-[j]-phenanthridinones has been developed using an aryne annulation strategy under metal-free reaction conditions. The reaction involves multiple C-C and C-N bond cleavages/formations through Diels-Alder reaction, aromatization-driven C-N bond cleavage, and amide formation.
Article
Chemistry, Organic
Pei Xie, Yating Zheng, Yuping Luo, Jinyun Luo, Leifang Wu, Zhihua Cai, Lin He
Summary: A facile and efficient method for the synthesis of sulfilimines through multicomponent reaction of arynes, sulfamides, and thiosulfonates was developed. This protocol showed good compatibility with structurally diverse substrates and functional groups, providing the corresponding sulfilimines in high yields. Mechanism studies revealed the key role of sulfenamide in the reaction.
Article
Chemistry, Organic
Matteo Lanzi, Racha Abed Ali Abdine, Maxime De Abreu, Joanna Wencel-Delord
Summary: This study reported the synthesis of dissymetric 2,3,2',3',4-substituted biaryls via pericyclic reactions of cyclic diaryl lambda(3)-bromanes. The method provides functional group tolerance and atom economy, allowing access to molecular complexity in a single reaction step. Continuous flow protocol has been designed for scale-up, while postfunctionalizations have been developed leveraging the residual Br-atom.
Article
Chemistry, Organic
Subarna Pan, Suparna Kundu, Rajarshi Samanta
Summary: This article describes a simple and efficient method for the synthesis of N-arylated 2-pyridone derivatives catalyzed by Rh(II), using 2-oxypyridine and diazonaphthoquinone as coupling partners. The reaction involves the insertion of the nitrogen atom of the 2-oxypyridine derivative into quinoid carbene and subsequent 1,6-benzoyl migratory rearrangement. The reaction exhibits broad scope and has the potential to provide axially chiral N-arylated 2-pyridone derivatives under suitable asymmetric conditions.
Article
Chemistry, Organic
Mengyang Shen, Jie Zhao, Yuanshuang Xu, Xinying Zhang, Xuesen Fan
Summary: This novel synthesis method of dihydroquinolinone derivatives involves an unprecedented cascade reaction, which includes the in-situ formation of aryne and its addition with pyrazolidinone, followed by N-N bond cleavage and intramolecular C-C bond formation. Compared to existing methods, this protocol offers advantages such as multiple transformations in one pot, a broad substrate scope, mild reaction conditions, and good tolerance of various functional groups. Additionally, the products obtained from this method demonstrated significant in vitro antiproliferative activity in selected human cancer cell lines.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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
Luyao Wang, Mengting Li, Zhitao Ning, Xi Zhang, Ying Fu, Zhengyin Du
Summary: An efficient visible-light-assisted, copper-catalyzed tandem radical cyclization of N-propargylindoles with cyclic ethers has been established. A series of 2-oxoalkyl-9H-pyrrolo[1,2-a]indol-9-ones with potential biological activities were synthesized in moderate yields using a dual catalytic system with copper acetate as a transition metal catalyst and eosin Y as a visible light catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Weiqiang Chen, Hui-Jing Li, Yun-Fei Cheng, Yan-Chao Wu
Summary: A C2-arylation reaction of N-acyl pyrroles using Pd(PPh3)(4) as a catalyst in combination with Ag2CO3 under air has been developed for the first time. This method provides a straightforward approach to the synthesis of valuable arylated pyrroles with good substrate tolerance and moderate to good yields under standard conditions. Interestingly, substrates with a thiophene or furan ring were found to be more reactive than pyrrole in the present catalytic system.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sanoop P. P. Chandrasekharan, Narendra Kumar Vaishanv, Ruchir Kant, Kishor Mohanan
Summary: A substrate-controlled reactivity switch was observed in the reaction of alpha-fluoro-beta-ketoamides with arynes. Secondary alpha-fluoro-beta-ketoamides reacted to afford alpha-aryl-alpha-fluoroacetamides through arylation/deacylation, while tertiary alpha-fluoro-beta-ketoamides underwent C-C sigma-bond insertion reaction to give 1,2-disubstituted arenes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xinyu Chen, Na Yang, Wen Zeng, Lei Wang, Pinhua Li, Hongji Li
Summary: A mild dearomative [5+2]/[2+2] cycloaddition of 1H-indoles with ortho-(trimethylsilyl)aryl triflates was reported, leading to the synthesis of dibenzo[b,e]azepine derivatives in moderate to good yields. Increasing steric hindrance at the C2-position of 1H-indoles directs the reaction towards a [2+2] cycloaddition pathway. Mechanistic investigations suggest that the reaction proceeds through a [2+2] cycloaddition followed by a ring expansion to form the [5+2] cycloaddition product.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Nicola L. Bell, Chao Xu, James W. B. Fyfe, Julien C. Vantourout, Jeremy Brals, Sonia Chabbra, Bela E. Bode, David B. Cordes, Alexandra M. Z. Slawin, Thomas M. McGuire, Allan J. B. Watson
Summary: A novel Cu-mediated C-N cross-coupling reaction has been identified in this study, which can be applied to drug synthesis and late-stage N-arylation. Mechanistic studies have provided evidence for the limitations in the methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fa-Chuang Liu, Meng-Jie Si, Xin-Ru Shi, Shi-Yi Zhuang, Qun Cai, Yi Liu, An-Xin Wu
Summary: A transition-metal-free formal (4 + 2) cycloaddition for the direct assembly of acridone derivatives has been developed using easily accessible o-aminobenzamides and 2-(trimethylsilyl)aryl triflates. The base plays a crucial role in the controlled synthesis of N-H and N-aryl acridones. Preliminary fluorescence studies show that N-aryl acridones can be used as fluorescent materials with a wide emission range.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Xiandong He, Feng Ye, Jia-Cheng Guo, Wenju Chang, Bingxu Ma, Riqing Ding, Sijing Wang, Yong Liang, Dehua Hu, Zi-Hao Guo, Yuguang Ma
Summary: In this study, a N-oxide building block, MeBTzO, was designed and synthesized by oxidizing sp(2)-N in the aromatic ring. Theoretical calculations revealed that MeBTzO exhibited higher reactivity in the direct (hetero)arylation polymerization (DHAP) compared to its non-oxide counterpart, MeBTz. PDPPMeBTzO, a conjugated semiconducting polymer containing N-oxide, was successfully synthesized via DHAP of MeBTzO with DPP. PDPPMeBTzO showed improved electron transport properties, with a higher mu(e) value of 0.11 cm(2) V-1 s(-1) compared to PDPPMeBTz (mu(e) = 7.49 x 10(-3) cm(2) V-1 s(-1)). This research demonstrates the potential of introducing N-oxide groups in conjugated polymers for high performance ambipolar and n-type CSP materials.
Article
Chemistry, Organic
Aranya Das, Sudipto Debnath, Poulami Hota, Tuluma Das, Dilip K. Maiti
Summary: Unprecedented metal-free cyclization catalysis reactions are developed to synthesize 3-amino-4-benzoyl biphenyls and arylacridones with high atom economy. Catalytic K2CO3 is used to achieve rapid dual C-C-coupled cyclization between beta-keto enamines and cinnamaldehydes, while molecular I-2 acts as a catalyst for C(sp(2))-H functionalized C-N bond-forming cyclization to yield valuable arylacridones. Plausible mechanisms for the new cyclization reactions are predicted through control experiments and ESI-MS analyses.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Baolei Wang, Marius-Georgian Constantin, Simarpreet Singh, Yuqiao Zhou, Rebecca L. Davis, F. G. West
Summary: Keto-substituted 1,2-cyclohexadienes were generated through base-mediated elimination and dimerized via an unprecedented formal hetero-Diels-Alder process, followed by hydration. These highly reactive cyclic allene intermediates showed high regio- and diastereoselectivity in Diels-Alder reactions, and could also react with enamine dienophiles in a hetero-Diels-Alder process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Satoshi Inouye, Mitsuhiro Nakamura, Takamitsu Hosoya
Summary: This study successfully demonstrates the enzymatic conversion of dCTZ to CTZ using NAD(P)H:FMN oxidoreductase, providing a new synthetic pathway for CTZ. Furthermore, the concentration of dCTZ can be determined by measuring the luminescence activity using CTZ-utilizing luciferases coupled with the FRase-NADH reaction.
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Rika Idogawa, Akihiro Kobayashi, Youngchan Kim, Ken Shimomori, Takamitsu Hosoya, Suguru Yoshida
Summary: An efficient method for sequential C-F transformations of o-hydrosilyl-substituted benzotrifluorides was developed, allowing for the synthesis of a wide variety of organofluorine compounds through successive reactions. Key to the success was the hydride reduction of o-fluorosilyl-substituted difluoromethylenes, enabling further C-F transformations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jumpei Taguchi, Kota Kimura, Kazunobu Igawa, Katsuhiko Tomooka, Takamitsu Hosoya
Summary: The generation of 3-azidoarynes from o-iodoaryl triflate-type precursors was achieved using a silylmethyl Grignard reagent as the activator. The azido group controls the regioselectivity of the reaction and can be further transformed into different nitrogen-containing compounds.
Article
Pharmacology & Pharmacy
Takayoshi Nakaoka, Ken-ichi Kaneko, Satsuki Irie, Aya Mawatari, Ami Igesaka, Yuta Uetake, Hidenori Ochiai, Takashi Niwa, Emi Yamano, Yasuhiro Wada, Masaaki Tanaka, Kohei Kotani, Hideki Kawahata, Joji Kawabe, Yukio Miki, Hisashi Doi, Takamitsu Hosoya, Maeda Kazuya, Hiroyuki Kusuhara, Yuichi Sugiyama, Yasuyoshi Watanabe
Summary: Uptake and efflux transporters play crucial roles in drug disposition. PET imaging is a useful tool for directly assessing drug transporter activity. A synthetic method for [18F]PTV, a PET probe for hepatobiliary transport, was developed. Rifampicin pretreatment significantly inhibited hepatic concentration and biliary excretion of the probe and decreased hepatic uptake clearance and canalicular efflux clearance. These results demonstrate the usefulness of [18F]PTV for investigating hepatobiliary transporters in humans.
DRUG METABOLISM AND PHARMACOKINETICS
(2022)
Article
Chemistry, Multidisciplinary
Akihiro Kobayashi, Tsubasa Matsuzawa, Takamitsu Hosoya, Suguru Yoshida
Summary: The interrupted Pummerer reaction of alkynyl sulfoxides with phenols is reported, leading to the efficient synthesis of various benz[b]furans through the unexplored electrophilic activation of the electron-deficient alkynyl sulfinyl group. Utilizing readily available alkynes, thiosulfonates, and phenols, we successfully prepared functionalized benz[b]furans.
Article
Chemistry, Multidisciplinary
Zhouen Zhang, Takashi Niwa, Kenji Watanabe, Takamitsu Hosoya
Summary: In this study, a two-phase radiosynthetic method for the ipso-C-11-cyanation of aryl fluorides was developed, using nickel-mediated C-F bond activation. A practical protocol was established that does not require a glovebox, making it applicable for general PET centers. This method enabled the efficient synthesis of diverse [C-11]aryl nitriles, including pharmaceutical drugs. Stoichiometric reactions and theoretical studies demonstrated the significant promotion effect of lithium chloride on the oxidative addition, facilitating rapid C-11-cyanation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Takashi Niwa, Tsuyoshi Tahara, Charles E. Chase, Francis G. Fang, Takayoshi Nakaoka, Satsuki Irie, Emi Hayashinaka, Yasuhiro Wada, Hidefumi Mukai, Kenkichi Masutomi, Yasuyoshi Watanabe, Yilong Cui, Takamitsu Hosoya
Summary: This study reports the successful 11C-radiolabeling of eribulin, an approved anticancer drug, which enables the quantitative measurement of eribulin migration into tumor tissue. The optimized synthetic method provides a reproducible way to produce [35-11C]eribulin with high radiochemical purity and molar activity. PET imaging using mice shows specific accumulation of [35-11C]eribulin in tumors without significant metabolic changes.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Multidisciplinary
Suguru Yoshida
Summary: We have developed selective methods for single C-F transformations of aromatic trifluoromethyl compounds, enabling us to prepare a broad range of organofluorines from simple benzotrifluorides through C-F and C-Si transformations. These methods include allylation using trityl cations, thiolation and azidation catalyzed by Yb(OTf)(3), as well as chlorination using trityl chloride. The resulting fluorosilyl group in these transformations can undergo further reactions such as protonation, halogenation, and Hiyama cross-coupling with C-Si cleavage. Additionally, benzyl fluorides can be synthesized through LiAlH4-reduction of the resulting fluorosilanes and further C-F transformations.
Article
Psychiatry
Manon Dubol, Jana Immenschuh, My Jonasson, Kayo Takahashi, Takashi Niwa, Takamitsu Hosoya, Sara Roslin, Johan Wikstrom, Gunnar Antoni, Yasuyoshi Watanabe, Mark Lubberink, Anat Biegon, Inger Sundstrom-Poromaa, Erika Comasco
Summary: The study investigated the availability of aromatase in healthy women before and after nicotine exposure. The findings suggest that nicotine acutely decreases aromatase availability in the thalamic area, indicating a potential mechanism mediating the effects of nicotine on human behavior.
COMPREHENSIVE PSYCHIATRY
(2023)
Article
Chemistry, Organic
Shinya Tabata, Mai Minoshima, Akihiro Kobayashi, Takamitsu Hosoya, Suguru Yoshida
Summary: Migrative thioamination of aryne intermediates using o-iodoaryl triflates and sulfilimines leads to the formation of highly functionalized o-thioaminated diaryl sulfides. The ring expansion of cyclic sulfilimines enables the synthesis of eight- and nine-membered organosulfur compounds from dibenzothiophene- and thianthrene-type sulfilimines, respectively.
Article
Chemistry, Organic
Jumpei Taguchi, Takumi Okuyama, Satomi Tomita, Takashi Niwa, Takamitsu Hosoya
Summary: An efficient method for producing 3-triazenylarynes from ortho-iodoaryl triflate-type precursors has been developed. The resulting arynes exhibit high regioselectivity in reactions with various arynophiles due to the presence of the triazenyl group. The 3-triazenylaryne precursors can be used as intermediates for the synthesis of diverse multisubstituted aromatic compounds through the transformation of the remaining triazenyl group in the aryne adducts and triazenyl group-directed ortho-C-H functionalization.
Article
Chemistry, Organic
Keisuke Nakamura, Yukiko Kumagai, Akihiro Kobayashi, Minori Suzuki, Suguru Yoshida
Summary: A practical method for synthesizing sulfinate esters from aryl iodides is presented, involving the direct oxidation of thioesters obtained through copper-catalyzed C-S formation. This efficient synthesis enables the preparation of a wide range of sulfinate esters using readily available starting materials such as carboxylic acids and anilines.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Koyo Numata, Shinya Tabata, Akihiro Kobayashi, Suguru Yoshida
Summary: An efficient synthetic method for multisubstituted naphthalenes has been revealed, involving the cycloaddition of 4-hydroxy-2-pyrones with aryne intermediates. Highly functionalized 2-pyrones were synthesized from 4-hydroxy-2-pyrones through a short synthetic route. The resulting 2-pyrones underwent smooth reactions with a variety of aryne intermediates, generated from o-silylaryl triflates. This led to the formation of multisubstituted naphthalenes via Diels-Alder reaction and subsequent decarboxylative aromatization. The aryne reaction of 2-pyrones also played a role in the synthesis of naphthalenes with 1,2,3-triazole moieties by combining with the triazole formation of 4-azido-2-pyrones.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kazuya Sugiyama, Yuki Sakata, Takashi Niwa, Suguru Yoshida, Takamitsu Hosoya
Summary: The iridium-catalyzed azide-thioalkyne cycloaddition proceeds faster with benzyl azide than with phenyl azide. Additionally, high azido-type selectivity is observed in other combinations of azides with different steric environments. This discovery enables efficient assembly of three azidophilic molecules to triazido platforms through three sequential triazole-forming reactions.
CHEMICAL COMMUNICATIONS
(2022)
