Article
Chemistry, Multidisciplinary
Laura Koering, Arne Stepen, Bernhard Birenheide, Simon Barth, Maxim Leskov, Roland Schoch, Felix Kraemer, Frank Breher, Jan Paradies
Summary: A series of redox-responsive ferrocenyl-substituted boranes and boronic esters were synthesized, and the oxidation of the ferrocenyl ligand to the ferrocenium increased the Lewis acidity beyond the strength of SbF5. This was investigated experimentally and computationally, and the resulting highly Lewis acidic boron compounds were used for catalytic C-F and S-F bond activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shivashankar Khanapur, Kenneth Lye, Dipendu Mandal, Xin Jie Wee, Edward G. Robins, Rowan D. Young
Summary: We present a general method for labeling both CF3 and CF2H groups in various chemical settings. The method provides good radiochemical yields and molar activities, and is applicable to biologically relevant compounds. The use of target compounds as starting materials and the simplicity of the method make it attractive for drug and radiotracer development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yue Zhao, Claire Empel, Wenjing Liang, Rene M. Koenig, Frederic W. Patureau
Summary: In this study, an unprecedented gem-difluoroallylation reaction of aryl sulfonium salts formed by direct functionalization was described. The method showed mild reaction conditions, wide applicability, and excellent selectivity.
Article
Chemistry, Applied
Satenik Mkrtchyan, Michal Jakubczyk, Suneel Lanka, Muhammad Yar, Khurshid Ayub, Mohanad Shkoor, Michael Pittelkow, Viktor O. Iaroshenko
Summary: In this study, two mild, solvent-free mechanochemical coupling transformations of CF3 group with nitro compounds were successfully demonstrated, leading to amides or Schiff bases. Ytterbia was used as a catalyst to facilitate the process, which involves C-F bond activation and the use of Si-based reductants/oxygen scavengers. This work represents the first example of utilizing mechanical energy to promote the transformation of the inert CF3 group into other functionalities.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Leidy V. Hooker, Jeffrey S. Bandar
Summary: This article summarizes the development and application of C-F bonds, focusing on the advantages of defluorination reactions in small molecule synthesis and illustrating how defluorofunctionalization can streamline synthesis and enable new reactions. The goal of the article is to educate chemists on the opportunities available for incorporating C-F bonds and exploiting their unique mechanistic pathways.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Leidy V. Hooker, Jeffrey S. Bandar
Summary: This review summarizes the advantages of defluorinative functionalization reactions for small molecule synthesis. It discusses the challenges, opportunities, and advances of defluorinative functionalization for different types of organofluorine compounds. Case studies are presented to illustrate the improvement of synthetic routes and the unique mechanisms and reactions enabled by C-F bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xinzi Pan, Maria Talavera, Gudrun Scholz, Thomas Braun
Summary: Chlorodefluorination reactions of fluoromethanes and fluoroolefins catalysed by nanoscopic aluminum chlorofluoride in the presence of ClSiEt3 were studied, showing successful conversion into chlorinated fluoro derivatives under mild reaction conditions. MAS NMR studies provided insights into the interaction between silanes, hexafluoropropene, and the ACF surface.
Article
Chemistry, Multidisciplinary
Mingjie Liu, Junnan Liu, Jing Li, Zhenghua Zhao, Kai Zhou, Yueming Li, Peipei He, Jiashu Wu, Zongbi Bao, Qiwei Yang, Yiwen Yang, Qilong Ren, Zhiguo Zhang
Summary: This study demonstrates a novel strategy to address the limitations of aryl-ketone photocatalysts in terms of photostability and photoinduced electron transfer applications. By incorporating symmetric aryl ketones into conjugated covalent organic frameworks, improvements in photostability, electronic transfer efficiency, and structure-performance relationships were observed. This system provides a robust rule of thumb for designing new-generation aryl-ketone photocatalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Ye Yuan, Muliang Zhang, Xiaodong Tang, Jared L. Piper, Zhi-Hui Peng, Jun-An Ma, Jie Wu, Fa-Guang Zhang
Summary: We have developed a photoredox platform that utilizes sulfinate as a radical-relay precursor and a sacrificial nucleofuge, allowing for the construction of styrenyl polyfluoro (hetero)arenes with branch selectivity. This protocol combines photoredox catalysis, radical-radical coupling, and an elimination process in a one-pot operation, providing a mild and efficient method to access polyfluoro (hetero)aryl derivatives of natural products and drugs.
Article
Chemistry, Multidisciplinary
Maria Talavera, Thomas Braun
Summary: The reaction of Rh(I) complexes with 1,1,3,3,3-pentafluoropropene yielded defluorinative germylation products and fluorido complexes. These complexes played a role in catalyzing derivatization reactions of 1,1,3,3,3-pentafluoropropene.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Chikako Matsuda, Ryo Igarashi, Hiroshi Katagiri, Takashi Murase
Summary: This study demonstrates that tri- and tetra-fluorinated [7]helicenes are photosensitive and undergo a double fluorine atom transfer. Furthermore, the transferred product undergoes a skeletal transformation on silica gel. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yu-Qing Ni, Dong-Jie Li, Yan Mei, Yan Jiang, Jun-Lei Zhang, Ke-Han He, Fei Pan
Summary: Here, we describe a base-mediated nucleophilic substitution reaction that efficiently synthesizes carbonyl-substituted gem-difluoroalkenes using simple silyl enol ethers. This protocol offers mild reaction conditions, a broad substrate scope, and scalability. Importantly, it demonstrates the applicability for late-stage functionalization of structurally complex molecules and provides valuable precursors for the synthesis of diverse medicinally relevant compounds.
Article
Chemistry, Organic
Yue Zhao, Bin Fu, Simin Wang, Yanfei Li, Xiuping Yuan, Jianjun Yin, Tao Xiong, Qian Zhang
Summary: A catalytic defluorinative boroarylation of alkenes with polyfluoroarenes and B(2)pin(2) was achieved using a PCy3-ligated copper catalyst. This method demonstrated good functional group compatibility and proceeded under mild reaction conditions, avoiding the need for stoichiometric quantities of organometallics. Valuable boronate-containing polyfluoroarenes, including challenging all-carbon quaternary carboncenter-containing triaryl alkylboronates, were efficiently synthesized.
Letter
Chemistry, Organic
Yue Zhao, Bin Fu, Simin Wang, Yanfei Li, Xiuping Yuan, Jianjun Yin, Tao Xiong, Qian Zhang
Summary: A catalytic defluorinative boroarylation of alkenes with polyfluoroarenes and B(2)pin(2) using a PCy3-ligated copper catalyst was developed. This method utilizes stable alkenes as latent nucleophiles and avoids the need for stoichiometric quantities of organometallics. It offers good functional group compatibility and operates under mild reaction conditions, enabling the efficient preparation of valuable boronate-containing polyfluoroarenes.
Article
Chemistry, Organic
Shao-Yong Chen, Yi-Chuan Zheng, Xu-Ge Liu, Jia-Lin Song, Lin Xiao, Shang-Shi Zhang
Summary: The indole-substituted trifluoromethyl sulfonium ylide was synthesized via the Cp*Rh(III)-catalyzed addition of diazocarbenoid to trifluoromethylthioether, and it represents the first example of an Rh(III)-catalyzed diazo-carbenoid addition reaction with trifluoromethylthioether. Several types of indole-substituted trifluoromethyl sulfonium ylide were prepared using mild reaction conditions. The method demonstrated high compatibility with functional groups and a wide substrate scope. Furthermore, it was found to be complementary to the method previously disclosed using a Rh(II) catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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
Kenji Watanabe, Asuka Kuratsu, Daisuke Hashizume, Takashi Niwa, Takamitsu Hosoya
Summary: We introduce a new method for amide bond formation based on the photoreaction of 3-acylindolizines with amines triggered by red-light irradiation. This method allows for the synthesis of conjugated amides in a short time with high yields. It is applicable to various aliphatic amines with different functional groups and can be conducted in aqueous organic solvents.
COMMUNICATIONS CHEMISTRY
(2022)
Article
Chemistry, Organic
Akito Katayama, Yuan Jin, Yoshitake Nishiyama, Takamitsu Hosoya, Satoshi Yokoshima
Summary: Treatment of alpha-azido sulfones with a thiol in the presence of 1,1,3,3-tetramethylguanidine leads to the formation of alpha-azido sulfides through sulfonyl group substitution. Experimental and DFT calculations suggest a reaction mechanism involving thiolate addition to the azido group and generation of an alkylidene triazene.
Article
Multidisciplinary Sciences
Satoshi Inouye, Jun-ichi Sato, Yuiko Sahara-Miura, Yuri Tomabechi, Yuto Sumida, Shun-ichi Sekine, Mikako Shirouzu, Takamitsu Hosoya
Summary: Oplophorus luciferase and its mutant nanoKAZ have been studied for their luminescence activity and substrate selectivity. QL-nanoKAZ showed higher luminescence intensity with CTZ than with bis-CTZ, making it a potential reporter protein for luminescence assay systems.
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)
