Article
Multidisciplinary Sciences
Jiayin Zhang, Xihao Chang, Xianghong Xu, Hongyi Wang, Lingzi Peng, Chang Guo
Summary: This study demonstrates the nickel-catalyzed dienylation and enantioselective allenylation of phosphine oxides, showing high selectivity in terms of chemo-, regio-, and enantioselectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shenghan Teng, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: Asymmetric coupling efficiently occurs between propargylic acetates, cycloalkenes, and electron-rich heteroarenes, yielding 2,3-disubstituted tetrahydrofurans and pyrrolidines in trans configuration with excellent enantiomeric ratios. The reaction proceeds via Wacker-type attack of nucleophilic heteroarenes on alkenes activated by allenyl Pd-II species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dandan Sun, Thayalan Rajeshkumar, Yifan Li, Jiaxin Xu, Runkai Chen, Zhaohua Wan, Zongchao Lv, Laurent Maron, Yi-Hung Chen
Summary: Transition-metal-catalyzed cross-coupling of propargylic electrophiles and Grignard reagents provides useful synthetic intermediates. However, few examples exist for the conversion of propargylic derivatives into propargyl compounds due to the challenging regioselectivity. We demonstrate a regioselective and stereospecific propargylation of Grignard reagents using LaCl3.2LiCl as a catalyst in the absence of a ligand.
Editorial Material
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: The cover of this issue features the research on the propargylic substitution reaction of propargylic alcohol with an N-monosubstituted hydrazone, where the nucleophilicity of the hydrazone is controlled by the choice of catalytic system. The full article can be accessed at 10.1002/chem.202103287.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Shiyao Liu, Yoshiaki Tanabe, Shogo Kuriyama, Ken Sakata, Yoshiaki Nishibayashi
Summary: In this study, propargylic substitution reactions using ruthenium and copper catalysis with N-monosubstituted hydrazones as ambident nucleophiles were investigated. It was found that N-monosubstituted hydrazones exhibited different reactivities depending on the catalytic system, resulting in either propargylic alkylated or aminated products. DFT calculations were used to study the reaction pathways and further transformation of the products yielded multisubstituted pyrazoles in good to high yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Wen-Ya Lu, Yong You, Ting-Ting Li, Zhen-Hua Wang, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: A new method for synthesizing allenyl thioether compounds via CuI-catalyzed decarboxylative thiolation of terminal alkyne-substituted cyclic carbonates/carbamates has been successfully developed. A variety of hydroxymethyl- and aminomethyl-containing allenyl thioethers were obtained in good to excellent yields under mild conditions. The copper-allenylidene intermediate plays a crucial role in the decarboxylative thiolation reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Sudeep Sarkar, Marcin Kalek
Summary: We have developed a metal-free method for the direct S-arylation of phosphorothioate diesters using diaryliodonium salts. This allows for the preparation of a wide range of S-aryl phosphorothioates, including complex molecules, as well as other arylated organophosphorus compounds. The reaction proceeds with retention of stereochemistry at the phosphorus atom, providing convenient access to P-chiral products. The mechanism of the reaction has been elucidated using DFT calculations.
Article
Chemistry, Inorganic & Nuclear
Yan Xu, Hong Yi, Martin Oestreich
Summary: This study reports a direct synthesis of enantioenriched allenylsilanes from racemic a-silylated propargylic bromides through an enantioconvergent nickel-catalyzed cross-coupling. The regioselectivity is controlled by the bulky silyl group, and the bond formation occurs exclusively at the y-position of the propargyl electrophile. The level of enantioselection induced by a chiral Pybox ligand is moderate.
Review
Chemistry, Multidisciplinary
Yong You, Yan-Ping Zhang, Zhen-Hua Wang, Jian-Qiang Zhao, Jun-Qing Yin, Wei-Cheng Yuan
Summary: Copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates are an efficient way to construct various useful skeletons. The field has gained attention and made significant progress due to the reaction sites of propargylic cyclic carbonates/carbamates and the advantages of copper catalysis. This review addresses the achievements, mechanisms, synthetic applications, limitations, challenges, and opportunities in this field.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Hui-Na Zou, Yu-Tao Zhao, Liang-Liang Yang, Ming-Yao Huang, Jing-Wei Zhang, Meng-Lin Huang, Shou-Fei Zhu
Summary: Chiral propargylic boron compounds have a wide range of potential applications, but the synthesis of these compounds with high enantioselectivity is still unknown. This study reports a catalytic method for the construction of chiral propargylic boron compounds with high enantioselectivity.
Article
Chemistry, Multidisciplinary
Xin Liu, Yibin Hu, Yuanbin She, Meichao Li, Zhenlu Shen
Summary: A green and practical electrooxidation protocol has been developed for the C3 acyloxylation of 2H-indazoles with carboxylic acids. The reaction is sustainable without the use of transition-metal catalysts and stoichiometric oxidants. Potassium carbonate plays a key role in the reaction and reacts with carboxylic acids to form carboxylates. The reaction proceeds via an ECE mechanism, and various carboxylic acids and 2H-indazoles can be used to generate novel products at room temperature in an undivided cell.
Article
Polymer Science
Catherine Marestin, Saber Chatti, Regis Mercier
Summary: Efforts have been made to synthesize phosphonic acid-containing poly(aryl ether)s (PAEs) by synthesizing two bisphenol monomers bearing phosphonic ester groups. The study identified specific experimental conditions to prevent side reactions and successfully prepared high molecular weight PAEs, which were further obtained containing free acid phosphonic groups through controlled hydrolysis.
Article
Chemistry, Applied
Seoyoung Lee, Juyeong Kim, Kyungjun Kang, Ansoo Lee, Hyunwoo Kim
Summary: In this study, we developed a ligand-controlled palladium-catalyzed allylic substitution approach that selectively achieves [1+1] and [1+2] allylic aminations between allylic diols and diamines. By combining this approach with sequential acetylation and allylic amination, tetraazamacrocycles with ring sizes ranging from 16 to 38 were successfully synthesized. These findings demonstrate the potential of a sequential allylation strategy for synthesizing complex molecules with broad applications in the fields of chemistry, pharmaceuticals, and medicine.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Ziying Wu, Miao Hu, Yangbin Jin, Jianxiao Li, Wanqing Wu, Huanfeng Jiang
Summary: Allylamines are valuable synthons due to their excellent reactivity in organic synthesis. An efficient amination reaction of allenyl ethers has been developed using copper/Lewis acid synergistic catalysis, providing access to diverse functionalized oxalylamines with high yields and selectivities. The method tolerates over 100 examples, including late-stage functionalization of bioactive molecules, and allows for gram-scale synthesis of oxalylamines under mild conditions with high turnover number. The applicability of the protocol is further demonstrated through the construction of drug molecules.
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, Multidisciplinary
Karol Kraszewski, Ireneusz Tomczyk, Aneta Drabinska, Krzysztof Bienkowski, Renata Solarska, Marcin Kalek
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Physical
Agata P. Perlinska, Marcin Kalek, Thomas Christian, Ya-Ming Hou, Joanna Sulkowska
Article
Chemistry, Organic
Sudeep Sarkar, Natalia Wojciechowska, Adam A. Rajkiewicz, Marcin Kalek
Summary: A metal-free arylation reaction using diaryliodonium salts and thiols has been developed. The C-S bond formation is achieved under mild and experimentally simple conditions with the application of a strong organic base. This method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from various thiols including aryl, heteroaryl, and alkyl thiols. The mechanism of the reaction was studied and determined to proceed via an inner sphere pathway involving the formation of an Ar2I(SR) intermediate, followed by reductive elimination.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Correction
Chemistry, Organic
Justyna Golebiewska, Jacek Stawinski
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Justyna Golebiewska, Agnieszka Bartoszewicz, Marcin Kalek, Jacek Stawinski
Summary: The study aims to explore the possibility of further functionalizing the sulfur or selenium heteroatoms in nucleotide analogues to create a second generation with new biological properties.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2022)
Article
Chemistry, Inorganic & Nuclear
Justyna Golebiewska, Jacek Stawinski
Summary: Nucleoside boranephosphonates are important nucleotide analogues with borane moiety, reacting with different types of amines to form various derivatives. Mechanistic studies revealed a common initial step leading to distinctive products depending on the type of amine used.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2022)
Article
Chemistry, Physical
Margot Jacquet, Silvio Osella, Ersan Harputlu, Barbara Palys, Monika Kaczmarek, Ewa K. Nawrocka, Adam A. Rajkiewicz, Marcin Kalek, Pawel P. Michalowski, Bartosz Trzaskowski, C. Gokhan Unlu, Wojciech Lisowski, Marcin Pisarek, Krzysztof Kazimierczuk, Kasim Ocakoglu, Agnieszka Wieckowska, Joanna Kargul
Summary: The covalent attachment of metalorganic wires on electron-rich surfaces, fluorine-doped tin oxide and single-layer graphene, leads to the promotion of p-doping of the graphene and significantly enhanced photocurrent, demonstrating potential applications in various fields.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Applied
Abhishek Pareek, Marcin Kalek
Summary: The Morita-Baylis-Hillman reaction utilizing N-alkylquinolinium salts as electrophiles has been developed. The reaction is catalyzed by DBU and involves regioselective dearomatization at the C-2 position, yielding a wide range of alpha-(1,2-dihydroquinolin-2-yl)vinyl esters, ketones, and sulfones. The scope of the reaction has been extended to N-alkylpyridinium salts, which require moderately electron-withdrawing substituents to achieve good reactivity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Biochemistry & Molecular Biology
Siva S. Panda, Marian N. Aziz, Jacek Stawinski, Adel S. Girgis
Summary: Azomethine ylides are frequently used three-atom components in nitrogen-based [3+2]-cycloaddition reactions with a variety of unsaturated 2 pi-electron components. These reactions demonstrate remarkable regio- and stereoselectivity and have attracted organic chemists' interest in constructing diverse heterocycles with four contiguous stereogenic centers. This review article summarizes the significant [3+2]-cycloaddition reactions of azomethine ylides with various olefinic, unsaturated 2 pi-electron components (acyclic, alicyclic, heterocyclic, and exocyclic ones) reported in the past two decades.
Article
Chemistry, Organic
Sudeep Sarkar, Marcin Kalek
Summary: We have developed a metal-free method for the direct S-arylation of phosphorothioate diesters using diaryliodonium salts. This allows for the preparation of a wide range of S-aryl phosphorothioates, including complex molecules, as well as other arylated organophosphorus compounds. The reaction proceeds with retention of stereochemistry at the phosphorus atom, providing convenient access to P-chiral products. The mechanism of the reaction has been elucidated using DFT calculations.
Article
Chemistry, Organic
Natalia Wojciechowska, Krzysztof Bienkowski, Renata Solarska, Marcin Kalek
Summary: Compared to chiral iodoarenes in organocatalysis, stoichiometric oxidants can be replaced by electric stimuli in electrosynthesis. By screening reaction parameters, an enantioselective electrochemical oxidation mediated by a chiral iodoarene has been achieved for the first time. However, the efficiency is relatively low due to the difficult electrochemical oxidation of the applied iodoarene catalyst.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Somayyeh Sarvi Beigbaghlou, Robert S. Yafele, Marcin Kalek
Summary: An electrochemical method for the oxidation of naphthols and phenols with intramolecular C-O bond formation has been developed. Optimization of reaction conditions allowed for the use of free phenols as starting materials instead of aryl methyl ether substrates. The reaction produces spirolactones and spiroethers in high yields up to 97% under simple experimental conditions without the need for catalysts or stoichiometric oxidants, and only hydrogen is generated as a byproduct.
SYNTHESIS-STUTTGART
(2023)
Article
Biochemistry & Molecular Biology
Mateusz Jedrzejewski, Barbara Belza, Iwona Lewandowska, Marta Sadlej, Agata P. Perlinska, Rafal Augustyniak, Thomas Christian, Ya-Ming Hou, Marcin Kalek, Joanna I. Sulkowska
Summary: The Nep1 protein plays a crucial role in the formation of small ribosomal subunits in eukaryotes and archaea, and it is responsible for the methylation of pseudouridine during pre-rRNA processing. Through a combination of bioinformatics, computational, and experimental methods, this study investigates the deprotonation of pseudouridine in the Nep1 active site by a distant aspartate residue. It identifies a potential proton-transfer mediator and confirms that both an amino acid and a water molecule can facilitate proton transfer, with the water-mediated pathway being the most favorable.
COMPUTATIONAL AND STRUCTURAL BIOTECHNOLOGY JOURNAL
(2023)
Article
Chemistry, Organic
Marta Rachwalak, Justyna Golebiewska, Tomasz Jakubowski, Jacek Stawinski
Summary: Boranephosphonate diesters can react with pyridine and some tertiary amines in the presence of dimethoxytrityl chloride as a borane hydride acceptor, to produce boron-modified phosphodiester analogues with a specific structural motif. Various aspects of the synthetic protocol, potential intermediates involved, and the role of solvents used are discussed.
SYNTHESIS-STUTTGART
(2021)
