Article
Chemistry, Multidisciplinary
Muriel Durandetti
Summary: The direct formation of C-C bonds catalyzed by nickel complexes has become an important research topic in the past fifty years, and has recently seen a resurgence as a new area in nickel chemistry. This paper provides a summary of the use of nickel complexes in catalysis and highlights the evolution of the authors' own research.
Article
Chemistry, Multidisciplinary
Kun Cui, Yan-Lin Li, Gongqiang Li, Ji-Bao Xia
Summary: A new regio- and stereoselective reductive coupling of alkynes and crotononitrile has been developed using visible light organophotoredox cobalt dual catalysis, resulting in the synthesis of enantioenriched homoallylic nitriles with stereodefined trisubstituted alkene.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Physical
Kuai Wang, Wangqing Kong
Summary: Organofluorine compounds have received significant attention in various industries due to their unique chemical and physical properties. However, the synthesis of these compounds still faces challenges, including difficulties in handling fluorinating reagents and controlling chemoselectivity. In recent decades, the development of Nickel-catalyzed defluorinative cross-couplings has provided powerful strategies for the construction of fluorinated organic compounds. This review summarizes important advances in this field, focusing on aryl fluorides, gem-difluorovinyl, and trifluoromethyl compounds.
Article
Chemistry, Multidisciplinary
Christopher S. Gravatt, Luis Melecio-Zambrano, Tehshik P. Yoon
Summary: The sole method available for the photocycloaddition of unconjugated aliphatic alkenes is the Cu-catalyzed Salomon-Kochi reaction. A new catalyst system with superior reactivity and photostability has been designed, offering significantly expanded substrate scope and highlighted through the preparation of the natural products sulcatine G and perforatol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Stavros K. Kariofillis, Abigail G. Doyle
Summary: In recent years, the development of light-driven reactions has made significant advancements in synthetic organic chemistry, particularly in combining photoredox and nickel catalysis for challenging cross-coupling reactions. The question of whether photo-induced activation of the nickel catalyst itself could lead to new approaches to cross-coupling has been explored. By utilizing a visible-light-driven mechanism for chlorine radical formation and conducting mechanistic investigations on organometallic Ni complexes relevant to cross-coupling, the study aims to facilitate new catalyst design and develop novel synthetic methods.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Stepan S. Tatevosyan, Yury N. Kotovshchikov, Gennadij Latyshev, Nikolay Lukashev, Irina P. Beletskaya
Summary: A convenient method for assembling 1,2,3-triazole-fused 4 H -3,1-benzoxazines has been developed, utilizing alcohol-tethered 5-iodotriazoles as precursors. The intramolecular C-O coupling proceeds efficiently under base-mediated transition-metal-free conditions, yielding cyclization products with up to 96% yield. This cost-effective procedure allows for a wide substrate scope and tolerates various functional groups.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Yangjinxiu Zhou, Tengfei Pang, Yu Liu, Fangrui Zhong, Guojiao Wu
Summary: We present a highly intriguing and underexplored multi-component reaction involving diazo molecules for polyene formation. This reaction involves coupling of 2,2,2-trifluorodiazoethane and aryl alkynes mediated by iodine under visible light. The reaction provides a straightforward and step-economic access to bistrifluoromethylated 1,3,5-trienes in high stereoselectivity by creating three C=C bonds in a single step under mild conditions.
Article
Chemistry, Multidisciplinary
Zhenghong Zhou, Jimin Yang, Bo Yang, Yang Han, Lijuan Zhu, Xiao-Song Xue, Feng Zhu
Summary: This study presents a pioneering example of nickel-catalysed enantioconvergent Stille cross-coupling reactions. The reactions result in the formation of C-C bonds in good to high yields with excellent stereoselectivity, providing a practical and cost-effective method for synthesis. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process, opening up new research possibilities in the field of Stille reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Masahiro Murakami, Naoki Ishida
Summary: This article reviews synthetic transformations involving the cleavage of a carbon-carbon bond of a four-membered ring from 2011 to 2019, with a particular focus on progress in catalytic reactions such as oxidative addition and beta-carbon elimination, as well as the increasing attention on beta-scission of radical intermediates. Additionally, Lewis acid-mediated and thermally induced ring-opening of cyclobutanone derivatives have garnered renewed interest, demonstrating the unique synthetic potentials of structurally strained four-membered ring compounds for constructing organic skeletons.
Article
Chemistry, Multidisciplinary
Andryj M. Borys, Eva Hevia
Summary: The Ni-catalysed cross-coupling of aryl ethers involves an anionic pathway, forming electron-rich hetero-bimetallic nickelates. The complexation chemistry between Ni(COD)(2) and PhLi leads to the discovery of a diverse family of catalytically competent lithium nickelates, with dramatic solvent and donor effects playing a crucial role in the catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Kamal M. Dawood, Ashraf A. Abbas
Summary: This article thoroughly reports the synthetic routes to six differently connected bipyrazole systems, with a focus on cyclocondensation reactions and 1,3-dipolar cycloaddition reactions. Many of these bipyrazoles have potential applications in pharmaceutical and material science fields.
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.
Review
Chemistry, Organic
Rida Noor, Ameer Fawad Zahoor, Syed Ali Raza Naqvi, Atta ul Haq, Rabia Akhtar
Summary: This review examines the synthetic routes attempted in the past two decades for forming large size carbocycles and heterocycles using ring expansion reactions, including lactams, boracycles, benzocycloheptenones, azaborinine, and azepine derivatives. Various rearrangement and cycloaddition reactions have been discussed.
SYNTHETIC COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shuai Liu, Pengchen Ma, Lu Zhang, Shenyu Shen, Hong-Jie Miao, Le Liu, K. N. Houk, Xin-Hua Duan, Li-Na Guo
Summary: An efficient alkoxyl radical-triggered ring expansion/cross-coupling cascade was developed under cheap metal catalysis. A wide range of medium-sized lactones and macrolactones were constructed in moderate to good yields, along with diverse functional groups. The proposed catalytic cycle for this tandem reaction involves Cu(i)/Cu(ii)/Cu(iii).
Article
Chemistry, Physical
Janet Bahri, Shubham Deolka, Pavan K. Vardhanapu, Eugene Khaskin, Ramadoss Govindarajan, Robert R. Fayzullin, Serhii Vasylevskyi, Julia R. Khusnutdinova
Summary: Versatile and practical light-promoted C-N and C-O cross-coupling reactions can be catalyzed by NiII complexes supported by 2,7-dimethyl-1,8-naphthyridine ligand, without the need for additional photocatalysts. These results highlight the potential of Ni naphthyridine complexes as a versatile catalytic motif for photoredox nickel catalysis.
Article
Biochemistry & Molecular Biology
Naoko Nakano, Kazuo Fukuda, Etsu Tashiro, Haruka Ishikawa, Waka Nagano, Rie Kawamoto, Alice Mori, Misao Watanabe, Ryu Yamazaki, Takahisa Nakane, Mikihiko Naito, Iwao Okamoto, Susumu Itoh
Summary: The study identified a compound, HK13, that interacts with YAP, a protein involved in malignant cancers. Hybrid compounds of platanic acid and LCL-161 were synthesized and one of them, HK24, showed inhibitory activity against the growth of YAP overexpressing lung cancer cells. It is possible that this activity is mediated by YAP degradation. Furthermore, the involvement of the proteasome pathway in HK24-dependent YAP degradation was confirmed.
JOURNAL OF BIOCHEMISTRY
(2022)
Article
Chemistry, Organic
Yusuke Kawasaki, Showkat Rashid, Katsuhiko Ikeyatsu, Yuichiro Mutoh, Yusukc Yoshigoe, Simko Kikkawa, Isao Azumaya, Shoichi Hosoya, Shinichi Saito
Summary: In this study, a series of [2]rotaxanes with various functional groups in the axle component were synthesized through the oxidativedimerization of alkynes mediated by a macrocyclic phenanthroline-Cu complex. The rotaxanes were fully characterized and the structure of one rotaxane was determined by X-ray crystallographic analysis. The interaction between the ring component and the axle component was studied in detail, revealing that the presence of a hydrogen bond between the phenanthroline moiety in the macrocyclic component and the acidic proton in the axle component influenced the conformation of the rotaxane.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Correction
Chemistry, Organic
Keisuke Takahashi, Shunya Kudo, Kiharu Kawamura, Taichi Kusakabe, Shoko Kikkawa, Isao Azumaya, Keisuke Kato
Article
Plant Sciences
Lingjian Tan, Kouharu Otsuki, Mi Zhang, Takashi Kikuchi, Misaki Okayasu, Isao Azumaya, Di Zhou, Ning Li, Li Huang, Chin-Ho Chen, Wei Li
Summary: Twelve macrocyclic daphnane diterpenoids, including six new compounds, were isolated from the whole plant of Daphne pedunculata. Their structures were determined using various methods, and their anti-HIV activity was evaluated. The compounds showed significant activity against HIV, providing further insights into the structure-activity relationships of macrocyclic daphnane diterpenoids.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Multidisciplinary
Showkat Rashid, Takashi Murakami, Hiroshi Koganezawa, Yusuke Yoshigoe, Shoichi Hosoya, Shinichi Saito
Summary: Oxidative dimerization of terminal alkynes (Glaser coupling) triggered by spirofluorene derived macrocyclic phenanthroline-Cu complexes was used to synthesize a series of novel [2]rotaxanes. The size and structural variations among the components and their effects on the dynamic behavior were investigated in detail using H-1 and F-19 NMR spectroscopy. Non-symmetric distribution of the ring component along the axle component was observed in the NMR spectra of rotaxanes with substituted macrocyclic components with low symmetry, and localization of the ring component near the 1,3-diyne moiety was observed in some [2]rotaxanes.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Ai Ito, Marino Asato, Yuki Asami, Kazuo Fukuda, Ryu Yamasaki, Iwao Okamoto
Summary: The conformations of aromatic amides bearing an N-(2-thienyl) or N-(3-thienyl) group were studied in both solution and crystal state. The NMR spectral data showed that the conformational preferences in solution depended on the pi-electron densities of the N-aromatic moieties and the three-dimensional relationship between the carbonyl oxygen and the N-aromatic moieties. Comparison of the preferences between N-(2-thienyl)amides and N-(3-thienyl)amides revealed that the Z-conformers of N-(2-thienyl)acetamides were stabilized by 1,5-type intramolecular S...O=C interactions. Crystal structures were similar to the solution structures. The estimated stabilization energy due to the intramolecular S...O=C interaction was approximately 0.74 kcal/mol and 0.93 kcal/mol for N-aryl-N-(2-thienyl)acetamides and N-methyl-N-(2-thienyl)acetamide, respectively.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ryu Yamasaki, Yuko Okada, Hiromi Iizumi, Ai Ito, Kazuo Fukuda, Iwao Okamoto
Summary: We report a facile transamidation of N-cyano amides with various amines at ambient temperature without any additive. Crystal analysis reveals that N-cyano amides prefer the trans conformation and exhibit reduced double bond character. DFT study suggests that the transamidation reaction proceeds via direct attack of amines on the carbonyl moiety.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Taiga Yasuda, Yusuke Yoshigoe, Shinichi Saito
Summary: This paper reports a concise synthesis of 1,8-diaminonaphthalene-protected diboronic acid (B2(dan)2), which is a promising borylating agent. B2(dan)2 is a stable compound that can be used for Cu-catalyzed borylation of styrene derivatives. The reaction shows high selectivity, and the products have yields up to 97%. Mechanistic studies suggest that a borate species is a key intermediate for the borylation reaction.
Article
Chemistry, Multidisciplinary
Masataka Ito, Yuriko Iwata, Hiroyasu Iwasaki, Kyu Hayashi, Taku Nakayama, Hidemasa Hikawa, Isao Azumaya, Hironori Suzuki, Shuji Noguchi
Summary: This finding suggests that deep eutectic solvents (DESs) can be utilized for the crystallization of cocrystals or salts from active pharmaceutical ingredients. In this study, DESs were employed as environmentally friendly solvents for crystal formation. The results revealed the formation of five different cocrystals or salts, including two that were identified for the first time.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Organic
Ryu Yamasaki, Mariko Ono, Kento Morita, Ai Ito, Kazuo Fukuda, Iwao Okamoto
Summary: Methyl substitution at the double bond of N-alkenyl anilides affects both the preferred conformation and susceptibility to acidic hydrolysis. Substitution at the R-1 position favors the trans conformation, while substitution at the R-2 or R-3 position favors the cis conformation. Substitution at the R-1 and R-3 positions increases the ratio of the trans conformer. DFT study reveals that these conformational preferences can be explained by torsion twisting induced by the substituent on the N-alkenyl moiety relative to the amide plane. R-1 substitution enhances susceptibility to acidic hydrolysis, while R-2 or R-3 substitution increases stability. The effect of the double bond on conformational preferences is demonstrated by comparing the preferred conformation of R-1-substituted anilide (trans) and hydrogenated N-isopropyl amide (cis).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Yusuke Yoshigoe, Keiichiro Hashizume, Shinichi Saito
Summary: Chiral aza-boraspirobifluorenes were synthesized and their structural and photophysical properties were evaluated. Enantiomers were separated by chiral HPLC and the absolute stereochemistry was determined. The racemization rate-determining step was found to involve the cleavage of the B-N bond.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Kenta Rakumitsu, Miho Fujii, Sotaro Kusumoto, Shoko Kikkawa, Isao Azumaya, Akihiro Yokoyama
Summary: A coronene amide analogue was synthesized using an improved method, and the palladium-mediated biarylation reaction played a key role in the synthesis.
Article
Chemistry, Multidisciplinary
Ryu Yamasaki, Misuzu Harada, Ai Ito, Kazuo Fukuda, Shota Matsumoto, Satoru Karasawa, Iwao Okamoto
Summary: A solvents-free molecular switch based on an amide skeleton was developed. The amide conformation was switched by treating the solid with HCl vapor and sublimation, and then reversed by sublimation with HCl removal. Crystal analysis confirmed the on/off process occurring in the gas state through sublimation rather than in the solution state.
Article
Chemistry, Multidisciplinary
Yusuke Yoshigoe, Yohei Tanji, Yusei Hata, Kohtaro Osakada, Shinichi Saito, Eiichi Kayahara, Shigeru Yamago, Yoshitaka Tsuchido, Hidetoshi Kawai
Summary: Different ligands can selectively generate different shapes of gold complexes. The dcpm ligand can accelerate the exchange reaction of Au(I)-CΣ bond to produce triangular macrocydic complexes. Additionally, the oxidative chlorination of the macrocydic gold complexes can yield a series of [n]cycloparaphenylenes in high yields.
Review
Chemistry, Multidisciplinary
Showkat Rashid, Yusuke Yoshigoe, Shinichi Saito
Summary: Advancements in mechanically interlocked molecular systems (MIMs) have reshaped the landscape of material chemistry and provided opportunities for exploring new applications and creating diversity. Among these molecular entities, rotaxanes have gained special attention in the field of supramolecular chemistry. This review aims to document the contemporary developments in the synthesis and applications of phenanthroline (phen) based rotaxanes.
