Article
Chemistry, Multidisciplinary
Farzaneh Karimi, Masoumeh Jadidi Nejad, Arefe Salamatmanesh, Akbar Heydari
Summary: A highly efficient heterogeneous copper catalyst was developed by supporting copper acetate on a magnetically separable triazine-vitamin B-5 system. The prepared nanoparticles were characterized by various techniques and showed favorable catalytic efficiency in the cyanation reaction of aryl halides using nitromethane as a non-toxic and cost-effective cyanation source. The magnetic nanocatalyst could be easily recovered and reused multiple times without significant performance decrease.
Article
Chemistry, Organic
Si-Zhan Liu, Jing Li, Cao-Gen Xue, Xue-Tao Xu, Lin-Sheng Lei, Chen-Yu Huo, Zhen Wang, Shao-Hua Wang
Summary: A copper-promoted cyanation of aryl iodides has been developed using N,N-dimethyl aminomalononitrile as the cyanide source, with moderate toxicity and good stability. This method exhibits a broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Mengna Liu, Benqiang Cui, Chuntao Zhong, Yanhui Shi, Yanfeng Dang, Changsheng Cao
Summary: A palladium-catalyzed cyanation of aryl dimethylsulfonium salts using K-4[Fe-(CN)(6)]center dot 3H(2)O as the cyanating reagent was successfully developed. The reaction proceeded under base-free conditions and yielded aryl nitriles with up to 92% yields. The protocol also allowed direct transformation of aryl sulfides to aryl nitriles, and the reaction mechanism was investigated using density functional theory calculations.
Article
Chemistry, Multidisciplinary
E. William Webb, Kevin Cheng, Jay S. Wright, Jocelyn Cha, Xia Shao, Melanie S. Sanford, Peter J. H. Scott
Summary: Radiocyanation is an attractive and complementary strategy for incorporating carbon-11 into radiotracer targets. This approach utilizes a Cu-11CN complex to capture aryl radical intermediates, enabling rapid and mild radiocyanation. Examples include the reaction of CuI with aryldiazonium salt and visible-light photocatalysis of aryl iodides, both followed by coupling with Cu-11CN to access challenging radiocyanated products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Miran Lemmerer, Haoqi Zhang, Anthony J. Fernandes, Tobias Fischer, Marianne Miesskes, Yi Xiao, Nuno Maulide
Summary: Herein, we present a method for the synthesis of alpha-aryl acrylamides through polar S-to-C aryl migrations induced by a Lewis basic organocatalyst. This polar process allows subsequent elimination reactions, leading to a formal aryl/hydrogen exchange, including SO2 extrusion. The reaction is selective for electron-deficient aromatic groups and can tolerate a variety of substituents on nitrogen and in the beta-position, providing useful building blocks for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Arvind K. Yadav, Srikanth Reddy Narra, Muhamad Zulfaqar Bacho, Yuji Sumii, Norio Shibata
Summary: A convenient method for the activation of aryl-oximes using TFEDMA as a scalable and efficient reagent is reported. Aryl-aldoximes led to aryl-cyanides, while aryl-ketoximes provided aryl-amides in moderate to excellent yields. The iminium form of TFEDMA acted as a fluorinated version of the well-known Vilsmeier reagent. Aryl cyanides and aryl amides are valuable synthetic units in natural products and drug candidates.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guangzhu Wang, Chaoren Shen, Xinyi Ren, Kaiwu Dong
Summary: An intramolecular Heck cyclization catalyzed by Ni/(S,S)-BDPP was developed for the synthesis of oxindoles with good enantioselectivities. The use of an electrophilic cyanation reagent was found to address the deleterious effect of the coordinative cyanide ion in asymmetric alkene arylcyanation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Taiga Mizushima, Marina Oka, Yasushi Imada, Hiroki Iida
Summary: The chemoselective electrochemical oxygenation of sulfides to sulfoxides is achieved using a biomimetic flavin catalyst that activates molecular oxygen under low cathode potential. Various functional groups are well tolerated under low-voltage electrolytic conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Materials Science, Ceramics
Kaan Karaoglu, Hakki Turker Akcay, Zehra Ozcifci, Melike Caliskan, Talat Baran
Summary: The Pd/Cr2O3 hybrid catalyst was synthesized and characterized for the cyanation reaction of aryl halides, showing good catalytic performance with a high yield of around 90% under optimal reaction conditions. The nano-sized structure of the Pd/Cr2O3 catalyst was protected without significant change after 5 cycles of catalytic activity, demonstrating its stability and effectiveness in the reaction.
CERAMICS INTERNATIONAL
(2021)
Article
Chemistry, Organic
Chunxiang Pan, Chunhui Yang, Kangkui Li, Keyang Zhang, Yuanbin Zhu, Shiyuan Wu, Yongyun Zhou, Baomin Fan
Summary: An efficient, catalyst/photocatalyst-free, and cost-effective methodology has been developed for the synthesis of beta,gamma-unsaturated nitriles from alpha,beta-unsaturated carboxylic acids. The reaction proceeded in an environmentally benign atmosphere of blue light-emitting diode irradiation with K2CO3 and water at room temperature, showing high yields (up to 83%) with a wide range of substrates.
Article
Chemistry, Multidisciplinary
Saikat Maiti, Joon Ho Rhlee
Summary: Stereoselective dicarbofunctionalization of terminal aryl alkynes has been achieved through reductive Ni-catalysis, utilizing alkyl iodide and aryl iodide as electrophilic coupling partners to accomplish exclusive regioselective and anti-addition selective alkylarylation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Tristan Delcaillau, Adrian Woenckhaus-Alvarez, Bill Morandi
Summary: A nickel-catalyzed cyanation method using Zn(CN)(2) as the cyanide source has been developed for the functionalization of aryl thioethers, involving both C-S bond activation and C-C bond formation. The combination of ligand dcype and base KOAc is crucial for the efficiency of this transformation. The scalability, low catalyst and reagent loadings, and high functional group tolerance make this reaction useful for late-stage derivatization and polymer recycling in organic chemistry.
Article
Chemistry, Multidisciplinary
Soumen Barik, Sayan Shee, Soumik Das, Rajesh G. Gonnade, Garima Jindal, Subrata Mukherjee, Akkattu T. Biju
Summary: This study describes the atroposelective synthesis of N-aryl succinimides with axially chiral C-N bonds catalyzed by N-heterocyclic carbenes, achieving good yields and ee values. Preliminary investigations were also conducted on the rotation barrier for the C-N bond, temperature dependence, and detailed DFT studies on the mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Wenjun Miao, Chuanfa Ni, Pan Xiao, Rulong Jia, Wei Zhang, Jinbo Hu
Summary: This novel nickel-catalyzed reductive cross-coupling reaction allows the formation of C(sp(2))-C(sp(2)) bonds through selective C(sp(2))-S bond cleavage, showcasing the new reactivity of 2-PySO2CF2H reagent. The use of readily available nickel catalyst and sulfones as coupling partners enables facile access to biaryls under mild reaction conditions without pregeneration of arylmetal reagents.
Article
Chemistry, Multidisciplinary
A. Hess, H. C. Guelen, N. Alandini, A. Mourati, Y. C. Guersoy, P. Knochel
Summary: This study presents a novel method for the selective ortho, ortho'-functionalization of readily available aryl oxazolines using sBu(2)Mg in toluene followed by trapping reactions with electrophiles. The conversions of these nitriles to valuable heterocycles are reported, and a tentative mechanism is proposed for the reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Applied
Masafumi Yano, Yoshinori Inada, Yuki Hayashi, Misaki Nakai, Koichi Mitsudo, Yukiyasu Kashiwagi
Summary: A triphenylamine compound with three benzothiophene rings was synthesized with a high yield, showing absorption at 386 nm and NIR-II absorption at 1213 nm after one-electron oxidation. This compound demonstrated a high fluorescence quantum yield and thermostability.
Article
Chemistry, Multidisciplinary
Eisuke Sato, Yuta Niki, Koichi Mitsudo, Seiji Suga
Summary: An oxidative trimerization of catechol and its derivatives leads to the formation of triphenylene derivatives. However, the precipitation of a radical cation pair during overoxidation hinders efficient synthesis. A reductive workup strategy and alternating current (AC) electrolysis offer effective solutions.
Article
Chemistry, Organic
Kyoko Mandai, Tetsuya Yamamoto, Hiroki Mandai, Aiichiro Nagaki
Summary: This study discovered that the reaction rate of cyclohexene epoxidation can be enhanced by using air as an oxidant without the need for added catalysts. A continuous flow reactor constructed with readily available stainless steel parts and devices was utilized, demonstrating a significant improvement in reaction time and high productivity. The efficient mass transfer between the liquid phase and air was the key factor in achieving the highly selective epoxide production.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hiroki Mandai, Yuichiro Matsuura, Fatin Mahfuzah Binti Johari, Koichi Mitsudo, Seiji Suga
Summary: An efficient method for silylation of alcohols using DMAPO as a reagent has been developed. Experimental results showed that the silylation of phenolic hydroxy group was much faster than that of primary alcohols, which might be attributed to the acidity (pKa value) of the hydroxy group.
Article
Chemistry, Organic
Koichi Mitsudo, Haruka Inoue, Yuta Niki, Eisuke Sato, Seiji Suga
Summary: This paper describes the electrochemical hydrogenation of enones using a proton-exchange membrane reactor. The reduction of enones proceeded smoothly under mild conditions to produce ketones or alcohols. The reaction showed chemoselectivity with the use of different cathode catalysts (Pd/C or Ir/C).
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Eisuke Sato, Sae Kangawa, Koich Mitsudo, Seiji Suga
Summary: The semi-pinacol rearrangement of tetrahydro-P-carbolines to afford 3-spirooxindoles was efficiently promoted by anodically generated bromonium ion equivalent as a halogen mediator.
Article
Chemistry, Applied
Eisuke Sato, Gaku Tachiwaki, Mayu Fujii, Koichi Mitsudo, Takashi Washio, Shinobu Takizawa, Seiji Suga
Summary: The use of a flow reactor in electrolysis allows for efficient and scalable synthesis, which is typically challenging with batch reactors. We successfully achieved electrochemical carbon-Ferrier rearrangement using catalytic anodic oxidation in an electrochemical flow reactor. Gaussian process regression (GPR), a machine learning method, enabled the adjustment of numerical parameters derived from the flow reactor. GPR also facilitated the construction of two models for estimating yields and productivity, allowing for rational selection of reaction conditions.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Organic
Koichi Mitsudo, Yasuyuki Okumura, Kotaro Yohena, Yuji Kurimoto, Eisuke Sato, Seiji Suga
Summary: Electrochemical dehydrogenative C-O bond formation was achieved for the synthesis of sultones. In the presence of K2CO3 and H2O, constant current electrolysis of [1,1'-biphenyl]-2-sulfonyl chloride resulted in quantitative formation of aryl-fused sultone. Control experiments suggest that electrochemical oxidation of sulfonates generates sulfo radical intermediates.
Article
Chemistry, Organic
Koichi Mitsudo, Keisuke Shigemori, Taro Shibata, Hiroki Mandai, Eisuke Sato, Seiji Suga
Summary: An electrochemical cross-coupling reaction between arylboronic esters and aryllithiums was developed, with the essential role of Br- in the electrolyte. NaBr was chosen as the electrolyte for its inexpensiveness and abundance, serving as a halogen mediator. Under mild conditions, the reaction yielded biaryls.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Eisuke Sato, Ayaka Yukiue, Koichi Mitsudo, Seiji Suga
Summary: Anodic oxidation was used to achieve the aromatization of 1,2,3,4-tetrahydrocarbazoles. Nitrogen-protected tetrahydrocarbazoles were converted to carbazoles with the use of bromide as a mediator. The presence of AcOH and the inexpensive bromide source LiBr allowed for efficient transformation.
Article
Electrochemistry
Eisuke Sato, Mayu Fujii, Koichi Mitsudo, Seiji Suga
Summary: In this study, the alkynylation of aldehydes initiated by cathodic reduction was investigated. It was found that only a small amount of catalytic current was needed to completely consume the starting material. Cyclic voltammetry and control experiments suggested that the electron-generated base from the cathodic reduction of benzaldehyde promoted the alkynylation reaction.
