Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Hua Yao, Xiaoyang Zhong, Bingqing Wang, Sen Lin, Zhaohua Yan
Summary: A novel and efficient approach for the amine-directed dehydrogenative C(sp(2))-C(sp(3)) coupling of arylamines with acetonitrile was developed using FeCl2 as the catalyst. The method provides a straightforward and green route to arylacetonitriles with good regioselectivity and excellent compatibility of functional groups and aromatic rings.
Article
Chemistry, Multidisciplinary
Jingyi Wang, Xuzhong Shen, Xu Chen, Yinwei Bao, Jian He, Zhan Lu
Summary: In this study, cobalt-catalyzed enantioconvergent cross-coupling of alpha-bromoketones with aryl zinc reagents was achieved, leading to the synthesis of chiral ketones with alpha-tertiary stereogenic centers. Ligand modification was found to be critical for improving the reactivity and selectivity of this transformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Dong Liu, Zhao-Ran Liu, Zhen-Hua Wang, Cong Ma, Simon Herbert, Hartmut Schirok, Tian-Sheng Mei
Summary: In this study, the authors investigated the electrochemical asymmetric catalysis by utilizing both the anode and cathode as working electrodes. The asymmetric cross-coupling between alpha-chloroesters and aryl bromides was successfully achieved, demonstrating the synergistic involvement of cathodic reduction and anodic oxidation in the paired electrolysis. This electrolytic method provides a promising alternative for asymmetric catalysis in organic synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jie Li, Xinhui Zhang, Yisen Yao, Yapei Gao, Wen Yang, Wanxiang Zhao
Summary: An efficient palladium-catalyzed Suzuki-Miyaura cross-coupling reaction has been developed for the synthesis of oxygen atom-substituted allylboronates with aryl/vinyl bromides, iodides, and triflates. This protocol offers a broad substrate scope, excellent functional group tolerance, and easy gram-scale preparation, providing an alternative approach for the synthesis of allylic alcohols and their derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shiyi Yang, Hengzhao Li, Xiang Yu, Jie An, Michal Szostak
Summary: A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using a very low loading of [Pd] in the presence of mild K3PO4 base under aqueous conditions. This operationally trivial protocol allows for the activation of C-O bond and is tolerant to various sensitive functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Qiang Wang, Shuaijie Wu, Yi-Dong Wang, Jing Sun, Ying Han, Chao-Guo Yan, Lei Wang
Summary: Here, a new and efficient strategy for the synthesis of alkenyl sulfoxides is reported. The method involves the transition metal-free C-S cross-coupling reaction between sulfenate anions and alkenylsulfonium salts. The in situ generation of sulfenate anions from beta-sulfinyl esters under mild conditions provides an effective approach for the synthesis of diverse alkenyl sulfoxides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Lucie Finck, Martin Oestreich
Summary: This article presents a general strategy for the synthesis of azobenzenes through an unprecedented C(sp(2))-N(sp(2)) cross-coupling reaction, using masked diazenes and aryl bromides. The reaction allows for the efficient preparation of azoarenes decorated with two aryl groups, with no loss of dinitrogen.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Rakesh Kumar, Irshad Maajid Taily, Prabal Banerjee
Summary: This paper describes a selective electrochemical method for the site-selective oxidation of arenes. The method enables the direct conversion of C(sp(2))-H bonds to aryl sulfides under mild reaction conditions without the need for external metals or oxidants.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Physical
Valentine P. Ananikov
Summary: Methods for direct one-step replacement of a hydrogen atom in a C-H bond by an organic functional group can create enormous possibilities for synthetic applications. The discovery of the reaction of organopalladium complexes with olefins has opened a new era in catalysis and organic chemistry.
Article
Chemistry, Organic
Han Byeol Kim, Hee Jin Jeong, Jae Eun Jung, Jae Kyun Lee, Duck-Hyung Lee, Seo-Jung Han
Summary: A mild, efficient, and transition-metal-free three-component coupling reaction involving arynes, phosphites, and aldehydes was established. It produced 3-mono-substituted benzoxaphosphole 1-oxides. A range of 3-mono-substituted benzoxaphosphole 1-oxides was obtained from both aryl- and aliphatic-substituted aldehydes in moderate to good yields. The reaction's synthetic utility was demonstrated by a Gram-scale reaction and the transformation of the products into various P-containing bicycles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
George Kwesiga, Julia Greese, Alexandra Kelling, Eric Sperlich, Bernd Schmidt
Summary: Isoflavones were synthesized via Suzuki-Miyaura coupling, and reliable conditions were identified using Pd(dba)2 as a precatalyst and tricyclohexylphosphine as an activating ligand. Higher yields were obtained with para-phenolboronic acid, suggesting the advantage of introducing substituents after the cross-coupling step.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
George Kwesiga, Julia Greese, Alexandra Kelling, Eric Sperlich, Bernd Schmidt
Summary: Isoflavones were synthesized via Suzuki-Miyaura coupling using para-phenolboronic acid and para-methoxybenzene boronic acid as reactants. The optimized conditions led to higher yields of isoflavones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Deepali Sharma, Aayushi Arora, Preeti Oswal, Anurag Bahuguna, Anupama Datta, Arun Kumar
Summary: This article introduces the methods and approaches of using organosulfur and organoselenium ligands to develop homogeneous, heterogeneous, and nanocatalysts, and critically analyzes the impacts of various factors on the catalytic reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Applied
Yasushi Yoshida, Tappei Fujimura, Takashi Mino, Masami Sakamotoa
Summary: This study reports an asymmetric synthesis method of chiral N,S-acetals using a chiral iodonium salt catalyst under neutral conditions, with good-to-excellent yields and enantioselectivities. The reaction mechanism and catalyst activation were studied through NMR experiments and DFT calculations, and the abnormal counteranion effect was also investigated.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Takumi Nakamura, Kazuma Ban, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: The study achieved asymmetric synthesis through photochemical reaction and crystallization-induced dynamic deracemization, demonstrating high enantioselectivity. Efficient deracemization was found achievable in the presence of a catalytic base in acetone under suitable conditions. Additionally, Viedma ripening technique can transform racemic indoline crystals into enantiomeric crystals with high enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Takumi Nakamura, Hiroki Ishikawa, Kazuma Ban, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: Atroposelective resolution of axially chiral nicotinamides was achieved through dynamic chiral salt formation with L-DBTA. Six types of nicotinamides that could not be optically resolved by preferential crystallization were studied. The kinetic analysis showed that the chiral conformation was retained for a significant period of time. Two methods of crystallization-induced asymmetric transformation, solvent evaporation and attrition-enhanced asymmetric transformation, were examined. The attrition method proved to be more effective for asymmetric amplification of diastereomeric salts of axially chiral materials.
Article
Chemistry, Applied
Isami Nakajima, Minori Shimizu, Yuta Okuda, Ryo Akiyama, Ryu Tadano, Masahiro Nagaoka, Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Hiraku Shinozaki, Tetsuya Yamamoto
Summary: In this study, a specific complex was synthesized and used as a catalyst to achieve the 1,2-addition reactions of organoboron compounds under base-free conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Kazutaka Sanada, Aoi Washio, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Summary: This article presents a method for chiral symmetry breaking of monoacylated meso diols and demonstrates its effectiveness through experiments and structural analysis. The results show that Viedma ripening can efficiently produce enantiomer crystals, achieving asymmetric expression and amplification of sugar derivatives without an external chemical chiral source. Additionally, the method is successfully applied to asymmetric desymmetrization of acyclic meso-1,2-diols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Takashi Mino, Toshiki Yamaoka, Kohei Watanabe, Chihiro Masuda, Shohei Kasano, Yasushi Yoshida, Ryo Takita, Yoshio Kasashima, Masami Sakamoto
Summary: P,olefin ligand/palladium catalyst systems can easily afford the corresponding 2-substituted 3-allylindole derivatives in good to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Norika Miyazaki, Kazutaka Sanada, Takumi Nakamura, Aoi Washio, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: The asymmetric amplification of p-anisoin was achieved using chiral amino acids as catalysts. Under basic conditions, p-anisoin crystallized as a conglomerate and underwent efficient deracemization through Viedma ripening. The chiral selectivity of the crystallization could be controlled by the coexistence of specific amino acids. L-amino acids favored the formation of (R)-anisoin crystals, while D-amino acids favored the formation of (S)-isomer crystals. This asymmetric transformation was attributed to the presence of enantiomeric amino acids in the mother liquor. Similar asymmetric transformations were observed in alpha-hydroxyketones such as acetoin.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Biochemistry & Molecular Biology
Yasushi Yoshida, Tatsuya Ao, Takashi Mino, Masami Sakamoto
Summary: In this study, chiral halonium salts with an N-nitrosamine moiety were developed and applied to the Mannich reaction. The novel bromonium salt catalyst showed high yields and up to 80% ee. This is the first catalytic application of N-nitrosamines.
Article
Chemistry, Organic
Takashi Mino, Kaho Takaya, Kaito Koki, Natsume Akimoto, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: We synthesized N-alkyl-N-cinnamoyl amide type phosphine-olefin compounds 1 and observed axial chirality in the C(aryl)-N(amide) bond of compounds 1 using HPLC analysis with a chiral stationary phase column. Enantiomeric isomers of 1 were obtained and (-)-1 was demonstrated as a chiral ligand in Pd-catalyzed asymmetric allylic substitution reactions, leading to high enantioselectivity (up to 97% ee) in the esterification process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Nobuo Yasuike, Chihiro Kachi-Terajima, Amir Karin, Takashi Mino, G. Andrew Woolley
Summary: Thiol-reactive reagents cannot be used for the modification of intracellular targets due to the presence of high concentrations of glutathione. This study proposes an equilibrium, entropic strategy using a cyanoacrylate-based thiol-reactive cross-linker to achieve target selectivity. The cross-linker shows high selectivity for reaction with target peptides and proteins containing paired thiols.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
