Article
Chemistry, Multidisciplinary
David Egea-Arrebola, F. Wieland Goetzke, Stephen P. Fletcher
Summary: Rhodium-catalyzed enantioselective additions of aryl and vinyl boronic acids to cyclobutenone ketals are described in this work. The reaction involves enantioselective carbometalation to give cyclobutyl-rhodium intermediates, followed by beta-oxygen elimination to afford enantioenriched enol ethers. Overall, this addition serves as a surrogate for Rh-catalyzed 1,4-additions to cyclobutenone.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Xu Wang, Jin-Ping Fu, Jia-Hui Mo, Yu-Hong Tian, Chun-You Liu, Hai-Tao Tang, Zi-Jun Sun, Ying-Ming Pan
Summary: The palladium-catalysed tandem cyclisation reaction successfully synthesizes a variety of 5-aminoimidazoles under mild conditions with high yields. This elegant domino process involves the effective cleavage of the N-O bond and the formation of new C-C and C-N bonds.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Tao Wang, Ji-Xun Guan, Yun-Xuan Tan, Ping Tian
Summary: This paper reports the first cobalt-catalyzed highly selective arylation carbocyclization reaction of 1,6-allenynes with arylboronic acids. The reaction demonstrates moderate to high yields, broad substrate scope, and good compatibility with functional groups.
Article
Chemistry, Applied
Juan C. Nieto-Carmona, Ines Manjon-Mata, M. Teresa Quiros, Gema Caballero-Santiago, Fernando Perez-Maseda, Diego J. Cardenas
Summary: In this study, we report the Ni-catalyzed cycloisomerization of 1,5-allenynes, which can yield different products depending on the substrates used. Internal alkynes can form fused bicyclic compounds, while those with terminal alkynes can generate cyclopentene derivatives. The mechanism of the reaction was also investigated and a catalytic cycle involving Ni(0)-Ni(II) species was proposed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Long Yin, Wanjiang Zhu, Yang Xu, Junhao Xing, Xiaowei Dou
Summary: The rhodium-catalyzed ring-opening coupling reaction of cyclic vinyl ethers, including 2,3-dihydrofuran and benzofuran, with organometallic reagents has been reported. The suitable organometallic reagent for 2,3-dihydrofuran and benzofuran was found to be dependent on the substrate, and a plausible mechanism involving different active organorhodium intermediates was proposed for these coupling reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Ignacio Medina-Mercado Susana Porcel
Summary: A gold-catalysed coupling reaction between aryldiazonium salts and arylboronic acids is described. The reaction proceeds efficiently under blue LED irradiation in the presence of KF and a catalytic amount of ascorbic acid, yielding satisfactory results. Notably, 4-nitrobenzendiazonium tetrafluoroborate exhibits sufficient reactivity to undergo the coupling reaction with various arylboronic acids even in the absence of aryl radical initiators. This coupling reaction is applicable for substrates with electron-donating and electron-withdrawing groups at the para, ortho, and meta positions.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Applied
Anastasia Kurbanova, Martin Nigrini, Kinga Golabek, Ondrej Vesely, Jan Vesely
Summary: Synthetic organic chemistry often requires multiple steps and expensive catalysts for the synthesis of functionalised tetrahydropyrans. In this study, we tested zeolites as eco-friendly and industrially relevant catalysts for the synthesis of 2-phenyltetrahydropyran. The results showed that zeolites favor the formation of the desired product, and the reaction kinetics depend on the number of acid sites, rather than the textural properties.
MICROPOROUS AND MESOPOROUS MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Nan Sun, Kai Zheng, Mingqiang Zhang, Guowen Zheng, Liqun Jin, Baoxiang Hu, Zhenlu Shen, Xinquan Hu
Summary: A mild Cu-catalysed Chan-Lam protocol has been developed for the synthesis of unsymmetrical aryl chalcogenides, including selenides and sulfides, in an aqueous micellar medium. The catalytic system consists of a CuBr catalyst, a water-soluble ligand, a surfactant, and air as the terminal oxidant. A diverse variety of diorganyl diselenides/disulfides could be coupled with various aryl, heteroaryl, and styryl boronic acids in water at ambient temperature to afford the corresponding aryl chalcogenide products in good to excellent yields. The aqueous phase can be recycled at least seven times by adding an additional half catalytic amount of CuBr during each subsequent cycle. UV-VIS spectral studies revealed the solubility of both hydrophobic diorganyl diselenides/disulfides and hydrophilic arylboronic acids in water with the help of the surfactant. Transmission electron microscopy studies showed the formation of nanomicelles under the reaction conditions.
Article
Chemistry, Applied
Jaroslav Pochobradsky, Jan Bartacek, Jiri Vana, Jan Svoboda, Marketa Svobodova, Pavel Drabina, Jan Patocka, Milos Sedlak
Summary: This study investigates the development of recyclable heterogeneous catalysts for the palladium-catalysed additions of arylboronic acids to nitrostyrenes. Two strategies, direct copolymerization and post-modification, are explored for immobilizing chiral isoquinoline-oxazoline ligands onto polymer matrices. The incorporation of polar functional groups into the polymer matrix enhances catalytic properties, albeit with a decrease in reaction rate compared to the homogeneous system. Post-modification using a polystyrenepolyethylene glycol (PS-PEG) support shows promise, resulting in a moderate decrease in reaction rate and satisfactory performance over multiple reaction cycles. These findings provide valuable insights into the immobilization of chiral ligands and highlight the advantages and limitations of different polymer compositions. The results contribute to the development of advanced catalytic systems for the synthesis of biologically relevant compounds.
REACTIVE & FUNCTIONAL POLYMERS
(2023)
Article
Chemistry, Physical
Qianqian Lu, Jun Gu, Fang Liu, Chunsen Li
Summary: In this study, density functional theory calculations were used to investigate the influence of tethered unsaturated carbon-carbon bond on the cycloisomerization mechanisms in rhodium(I)-catalyzed reactions of 1,6-allenynes. The results showed that distinct regioselectivity between alkene and alkyne insertions and the contrasting reactivity of rhodium-alkyl and rhodium-alkenyl intermediates contribute to the divergent cycloisomerization mechanisms. Further analysis revealed the effects of alkyne substituent and carbon chain length of the reactant on product selectivity.
Article
Chemistry, Organic
Matthew B. Minus, Sarah R. Moor, Fathima F. Pary, L. P. T. Nirmani, Malgorzata Chwatko, Brandon Okeke, Josh E. Singleton, Toby L. Nelson, Nathaniel A. Lynd, Eric Anslyn
Summary: The bimetallic methodology described in the study takes advantage of the distinct reactivities of palladium and copper to perform high yielding aryl-aryl dimerizations and polymerizations under ambient conditions. The process is facile and can be performed by simple mixing in an open vessel. This method demonstrates its utility in polymer synthesis by successfully creating various polymers at ambient temperature and open to air.
Article
Chemistry, Organic
Chun-Hua Yang, Xiangkun Sun, Congcong Niu, Zhiwei Zhang, Mingzhu Liu, Fangjie Zheng, Ling Jiang, Xiangtao Kong, Zhantao Yang
Summary: This metal-free reaction method allows the construction of different valuable compounds based on the substituents of the allene, with conjugative and sterically hindered phenyl groups favoring the formation of 3,5-dihydroazepine derivatives.
Article
Chemistry, Applied
Moreshwar B. B. Chaudhari, Prachi Gupta, Patricia Llanes, Miquel A. A. Pericas
Summary: The enantioselective Pictet-Spenlger reaction of tryptamines and diketo compounds catalyzed by a polymer-supported phosphoric acid (TRIP) has been achieved for the first time in continuous flow. A diverse library of quaternary tryptolines has been synthesized in 36-95% yield with 39-99% enantiomeric excess using this approach. The scalability of the reaction has been demonstrated in continuous flow, with a residence time of only 24 minutes. The robust immobilized catalyst has been recycled and reused multiple times in both batch and flow reactions. Synthesis of chiral precursors of Tadalafil, Iboga-type alkaloid (+)-Tabertinggine, and antimalarial spiroindolinones has been successfully achieved in both batch and continuous-flow reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Inorganic & Nuclear
Mathews Alisha, Rose Mary Philip, Gopinathan Anilkumar
Summary: This article provides a comprehensive review of rhodium-catalysed Heck type reactions, including oxidative, decyanative, desulfitative, decarbonylative Heck reactions, and even Heck type cyclizations, covering literature until 2021.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Hamilton C. Zimba, Lucas L. Baldassari, Angelica Moro
Summary: This study reports the development of a catalytic one-pot process, discussing the challenges and advantages encountered throughout. A regioselective, environmentally friendly, and operationally simple method was developed to explore the reactivity of functionalized propargylic alkynes through three copper-catalysed reactions in a single reaction vessel. The sequence involved hydroboration, azidation, and 1,3-dipolar cycloaddition, resulting in the regioselective formation of vinyl 1,2,3-triazoles in good yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Naoki Ishida, Yoshiki Kamae, Keigo Ishizu, Yuka Kamino, Hiroshi Naruse, Masahiro Murakami
Summary: The system described in the passage utilizes solar energy to capture, store, and release chemical energy for hydrogenation. Through a two-step process, solar energy is converted into chemical energy, which is then used for hydrogenation, with the advantage of easy recovery and reuse.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Tairin Kawasaki, Tomohiro Tosaki, Naoki Ishida, Masahiro Murakami
Summary: An alternative method has been developed for obtaining aryl esters from aliphatic primary alcohols and phenols using visible light irradiation at ambient temperature. The reaction does not require any oxidant or hydrogen acceptor, and successfully esterifies primary alcohols with various functional groups with phenols. The produced esters can be used as precursors for various carbonyl compounds.
Article
Chemistry, Organic
Naoki Ishida, Mingon Son, Tairin Kawasaki, Misato Ito, Masahiro Murakami
Summary: The photoinduced dehydrogenative homocoupling reaction of alkylarenes is an environmentally friendly and atom-economical method for forming sterically strained C-C single bonds, without the need for oxidants or hydrogen acceptors. This reaction serves as a remarkable example of photodriven reactions overcoming the use of considerable energy.
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
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
Yusuke Masuda, Masumi Uno, Masahiro Murakami
Summary: This study reports a photoinduced reaction of triarylphosphines with alkenes in the presence of carbonic acid, leading to the formation of fused tricyclic phosphonium salts with a phosphatricyclo[4.3.0.0(2.9)]nonene core structure. The reaction involves dearomatizing transannulation of the phenyl ring, 1,2-migration of the phosphorus atom, and incorporation of an alkene, being promoted by cooperation of visible light with a photocatalyst under mild reaction conditions.
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
Chemistry, Organic
Daichi Ikeshita, Yusuke Masuda, Naoki Ishida, Masahiro Murakami
Summary: A photoinduced hydrophosphination reaction of terminal alkynes with tri(o-tolyl)phosphine to form alkenylphosphonium salts is reported herein. This sustainable reaction eliminates the need for complex starting materials and expensive transition metals. The o-methyl groups of tri(o-tolyl)phosphine serve two important roles in guiding the phosphorus radical addition onto the terminal sp carbon and intramolecular hydrogen atom transfer.
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
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)
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)
