Article
Chemistry, Organic
Sajid Ur Rehman, Changkun Li
Summary: A highly regio- and enantioselective allylic sulfonation was achieved by using rhodium and bisoxazolinephosphine (NPN*) ligands, starting from racemic branched allylic carbonates and readily available sulfonylhydrazides under neutral conditions. The reaction produced branch-selective allylic sulfones with a >20:1 branch:linear ratio and >99% enantiomeric excess (ee) in <= 96% yield. Both Z and E linear allylic carbonates could also be transformed into the same chiral branched allylic sulfones with high regio- and enantioselectivities.
Article
Chemistry, Organic
Philip J. Smith, Yubo Jiang, Zixuan Tong, Helena D. Pickford, Kirsten E. Christensen, Jeremy Nugent, Edward A. Anderson
Summary: A novel transformation of alkynylyndiamides to tetrahydropyrrolopyrroles is reported, highlighting their potential utility in medicinal chemistry.
Article
Chemistry, Organic
Caterina Squizatto, Maira A. Bianchini, Carina M. L. Delpiccolo
Summary: A versatile one-pot strategy for the synthesis of compounds of synthetic interest has been presented. The strategy involves the transannulation of N-sulfonyltriazoles through alkenes and rhodium catalysis, yielding 2,3-dihydropyrroles. The evaluation of different alkenes and the use of minimal solvent are highlighted. The method also allows for the modulation of N-sulfonyltriazoles to selectively obtain cyclopropyl tosylimines or 2,3-dihydropyrroles. The potential of the methodology is demonstrated through the synthesis of structurally diverse analogues and late-stage transformations of bioactive molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guolin Wu, Yuan Yao, Gen Li, Xue Zhang, Hui Qian, Shengming Ma
Summary: This study developed a catalytic recipe of copper halides to address the issues of side reactions and selectivity in the 1,5-H transfer of alka-1,4-diyn-3-yl amines, providing various allenynes with excellent enantioselectivities. The method was successfully applied to the first highly enantioselective total synthesis of the natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5-H transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Qiuxia Jiang, Anquan Li, Xiang Liu, Yue Yu, Baofu Zhu, Hua Cao
Summary: An efficient and metal-free approach for synthesizing diverse functionalized furan derivatives using ene-yne-ketones and 1,3,5-triazinanes has been developed. This atom-economical and environment-friendly protocol allows for selective C-N and C-O bond formation in polysubstituted furans in a one-pot reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Rongxiang Chen, Yaoxue Tang, Xiaohui He, Kai-Kai Wang, Lina Ding, Lantao Liu
Summary: A copper/cobalt-catalyzed difunctionalization of alkenes with sulfonylazides and tert-butyl hydroperoxide has been developed for the efficient synthesis of β-ketosulfones and β-sulfonyl peroxides. This protocol offers moderate to good yields under mild conditions and features a wide substrate scope and good functional group tolerance. Sulfonylazides are used as a new sulfonyl radical source in this methodology.
Article
Chemistry, Multidisciplinary
Xiaobo Pang, Zhen-Zhen Zhao, Xiao-Xue Wei, Liangliang Qi, Guang-Li Xu, Jicheng Duan, Xue-Yuan Liu, Xing-Zhong Shu
Summary: A reductive approach for branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R-X electrophiles is reported in this study, showing a new selectivity pattern for diene functionalization. The combination of Ni(0) and the phosphine-nitrile ligand resulted in >20:1 regioselectivity, allowing for the conjugation of two biologically active units to form more complex polyene molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Kai Ji, Ka Lu, Jie Huang, Zi-Hao Li, Hua Ke, Zhi-Min Chen
Summary: A Bronsted acid-catalyzed 1,4-addition hydrothiolation of branched 1,3-dienes was explored for the first time, along with a solvent-controlled divergent synthesis of sulfides. The study showed that the choice of solvent influenced the type of products obtained, with acetonitrile yielding allylic sulfides and dichloromethane yielding thiochromane derivatives. The regioselectivity of hydrothiolation was investigated using density functional theory calculations.
Article
Chemistry, Organic
Shinnosuke Kurita, Sayori Kiyota, Nobuyuki Komine, Masafumi Hirano
Summary: A reliable method for preparing polysubstituted pyrroles from conjugated iminohexatrienes has been discovered. The reaction involves a Ru(0)-catalyzed cross-dimerization of iminoalkyne with conjugated dienes, followed by treatment with acetic acid to yield 2-alkenylpyrroles.
Review
Chemistry, Multidisciplinary
Mohammad Taghi Nazeri, Ahmad Shaabani
Summary: Pyrroles are important compounds found in many commercial drugs, biological composition, natural compounds, agrochemicals, and functional materials. The use of isocyanide-based multicomponent reactions (I-MCRs) for pyrrole synthesis is an efficient and eco-friendly approach that holds significance in the fields of organic chemistry and pharmaceutical chemistry.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Andrey Bubyrev, Ksenia Malkova, Grigory Kantin, Dmitry Dar'in, Mikhail Krasavin
Summary: A three-component synthesis of 1,5-disubstituted 1,2,3-triazoles can be achieved from alpha-acetyl-alpha-diazomethane sulfonamides, primary aliphatic amines, and aromatic aldehydes. The synthesis can proceed in two alternative variants based on the substitutions in the diazo reagent. Depending on the variant, the intermediates are either isolated and subjected to aromatization, or both transformations take place in a single step at room temperature.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Takuya Shimbayashi, Taiyou Ishige, Ken-ichi Fujita
Summary: A novel synthetic method for polysubstituted pyrroles from isocyanides and alpha,beta-unsaturated ketones using a rhodium catalyst and bis(pinacolato)diboron (B2pin2) is described. The selectivity for different pyrrole products can be controlled by adjusting the reaction temperature and isocyanide concentration. The 2-imidoylpyrroles obtained can be hydrolyzed to isolate 2-formylpyrroles, which are naturally abundant and useful in synthesis. Deuterium-labelling experiments suggest that rhodium hydride intermediates are involved in the catalytic cycle.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Issa Yavari, Meysam Ghorbanzadeh, Somayeh Akbarzadeh
Summary: A new strategy for the construction of functionalized 2-amino-3-cyano pyrroles has been developed, which involves a copper-catalyzed azide-alkyne cycloaddtion reaction followed by generation of N-sulfonoketenimine intermediates. The reaction proceeded smoothly in THF at ambient temperature to afford the target compounds in good yields and regioselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Geetanjali S. Sontakke, Kuntal Pal, Chandra M. R. Volla
Summary: In this study, we revealed substrate-dependent rearrangements of 4-substituted N-sulfonyl-1,2,3-triazoles under Rh(II)-catalysis via denitrogenation. The reaction involved the formation of an intermediatory phenonium ion and led to different scaffolds depending on the substituent present. The developed methodology features simple reaction conditions, excellent functional group compatibility, and broad substrate scope.
Article
Chemistry, Multidisciplinary
Wu-Bo Du, Ning-Ning Wang, Chao Pan, Shao-Fei Ni, Li-Rong Wen, Ming Li, Lin-Bao Zhang
Summary: An electrooxidative direct difunctionalization of internal alkynes with sulfonyl hydrazides has been developed for the construction of sulfonated enethers. This method does not require metal catalysts or stoichiometric amount of oxidants, and only yields molecular nitrogen and hydrogen as byproducts, providing a simple and green approach. The protocol can be efficiently scaled up, and the follow-up procedures of the corresponding functionalized alkenes demonstrate the practicality of the electrochemical synthesis.
Article
Chemistry, Multidisciplinary
Tomoya Miura, Shunsuke Moritani, Yota Shiratori, Masahiro Murakami
Summary: A unique method for the synthesis of substituted 1-naphthols through rhodium(ii)-catalysed ring-expansion reaction of 2-triazolyl-1-indanone derivatives is reported. The 1,2-acyl migration occurs with an intermediate alpha-imino rhodium carbenoid generated from the triazolyl moiety.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Yumi Ishihara, Takayuki Nakamuro, Shunsuke Moritani, Yuuya Nagata, Masahiro Murakami
Summary: This study investigates the asymmetric cyclooligomerization of bifunctional monomers catalyzed by rhodium(II). The major products obtained are cyclic dimers with unique structures, and it is observed that these structures can undergo ring-flipping.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Naoki Oku, Masahiro Murakami, Tomoya Miura
Summary: This article introduces a Suzuki-Miyaura cross-coupling reaction of alpha-chloroacetates or alpha-chloroacetamides with arylboronic acids under visible-light irradiation, providing a mild method for the synthesis of alpha-arylacetates and alpha-arylacetamides. Additionally, the authors successfully synthesized a key intermediate of the plant hormone auxin, indole-3-acetic acid derivative, from 1-Boc-indole in two steps by combining an iridium-catalyzed C-H borylation and a palladium-catalyzed cross-coupling reaction.
Article
Multidisciplinary Sciences
Junfei Xing, Keishi Takeuchi, Ko Kamei, Takayuki Nakamuro, Koji Harano, Eiichi Nakamura
Summary: With the development of atomic resolution transmission electron microscopy (AR-TEM), chemists can visually study the temporal evolution of molecular motions and reactions at the atomic level. However, experimental TEM images often differ from conventional molecular models, making them difficult to interpret. By introducing correlated atomic radii models, researchers can more easily estimate molecular structures from TEM images.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Multidisciplinary Sciences
Dongxin Liu, Satori Kowashi, Takayuki Nakamuro, Dominik Lungerich, Kaoru Yamanouchi, Koji Harano, Eiichi Nakamura
Summary: There is increasing attention to the chemical applications of transmission electron microscopy, but it is often hindered by radiation damage. This study focuses on the radiolysis damage in organic matter and aims to provide fundamental information on the product structure, electron energy influence, and reaction kinetics. By studying the [2 + 2] dimerization of a van der Waals dimer [60]fullerene in a carbon nanotube, the researchers identify five reaction pathways that serve as mechanistic models of radiolysis damage. The results highlight the importance of variable-temperature and variable-voltage kinetic analysis in understanding radiation damage mechanisms.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Takayuki Nakamuro, Ko Kamei, Keyi Sun, Jeffrey W. Bode, Koji Harano, Eiichi Nakamura
Summary: The study shows that the DP molecule has an intrinsic property of forming tetramers in water, which is enhanced by the presence of calcium ions. The dimer remains as the major species, and a face-to-face stacked structure based on dynamic imaging has been proposed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Olivier J. G. L. Chevalier, Takayuki Nakamuro, Wataru Sato, Satoru Miyashita, Takayuki Chiba, Junji Kido, Rui Shang, Eiichi Nakamura
Summary: This article describes the synthesis of lead bromide perovskite magic-sized nanoclusters via self-organization and their structural and dynamic properties revealed by electron microscopy. The study found that these nanoclusters exhibited quantum effects and minimal structural defects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Masaya Sakakibara, Hiroki Nada, Takayuki Nakamuro, Eiichi Nakamura
Summary: Operando imaging experiments conducted in carbon nanotubes revealed the metastable process of crystal nucleation, with a floating island (FI) identified as the first intermediate on the surface of NaCl crystals undergoing thermal migration. Tumbling of the crystal repeatedly changes the surface energy, promoting the conversion of FI into a new epitaxial layer.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Keiichi Irifune, Ken Yamazaki, Takayuki Nakamuro, Masahiro Murakami, Tomoya Miura
Summary: A ligand-controlled regiodivergence in Ni-catalyzed rearrangement of vinylcyclopropanes to 1,4- or 1,5-disubstituted cyclopentenes is reported. The 1,4- or 1,5-disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six-membered η(1)-allyl intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Naoki Oku, Tomoya Miura
Summary: A double C(sp3)-H functionalization of ethylarenes with alcohols and N- fluorobenzenesulfonimide is demonstrated. The reaction proceeds in three stages: (1) Cu-catalyzed benzylic alkoxylation of ethylarenes to give 1-(1-alkoxyethyl)benzenes; (2) The resulting 1-(1-alkoxyethyl)benzenes gradually convert into vinylarenes; (3) Cu-catalyzed amino-alkoxylation of the intermediary vinylarenes to yield arylethanolamines. This method introduces C-N and C-O bonds regioselectively at the homobenzylic and benzylic positions of ethylarenes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Toru Ishikawa, Fumihiko Tanaka, Kosuke Kurushima, Akira Yasuhara, Ryusuke Sagawa, Tatsuya Fujita, Ryohei Yonesaki, Katsuhiko Iseki, Takayuki Nakamuro, Koji Harano, Eiichi Nakamura
Summary: Carbon fiber obtained by pyrolysis of polyacrylonitrile exhibits superior properties for various applications, such as aircraft manufacture and power turbine blades. The structure of polyacrylonitrile-derived carbon fiber consists of hierarchically piled up wavy graphene-like networks, which exhibit high tensile strength and resistance to fracture. Conversely, pitch-based carbon fiber, consisting of crystalline graphene networks, is brittle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yusuke Masuda, Daichi Ikeshita, Kosuke Higashida, Masaki Yoshida, Naoki Ishida, Masahiro Murakami, Masaya Sawamura
Summary: Under photocatalytic conditions, tri(t-butyl)phosphine and terminal alkynes undergo 1,2-phosphorus-migrative [3 + 2] cycloaddition in the presence of a proton source. The reaction shows broad functional group tolerance and yields substituted cyclic phosphonium salts that can be further derivatized by Wittig olefination. Theoretical studies suggest that the phosphorus 1,2-migration of a β-phosphonioalkyl radical proceeds through a phosphine radical cation-alkene complex as a pseudointermediate, with the two fragments in the intermediate bound to each other through multiple noncovalent interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Keito Fuke, Tomoya Miura
Summary: This study reports a regioselective approach for the 1,2-hydro(cyanomethylation) of unactivated aliphatic alkenes. A cyanomethyl radical is added onto alkenes to form alkyl radicals, which then undergo further reactions to produce one-carbon-extended nitriles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Takayuki Nakamuro, Ko Kamei, Keyi Sun, Jeffrey W. Bode, Koji Harano, Eiichi Nakamura
Summary: The study demonstrates that Daptomycin molecules have the ability to self-aggregate in water, with stronger aggregation in the presence of calcium ions. By using structural analysis and dynamic imaging techniques, it was found that DP molecules primarily form dimers and tetramers, with a proposed structure model.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
