Article
Chemistry, Organic
Tomoki Yoshida, Takuya Kodama, Mamoru Tobisu
Summary: The rhodium-catalyzed decarbonylation of acylsilanes proceeds through the cleavage of a carbon-silicon bond. When two different acylsilanes are reacted in one batch, crossover products are formed, indicating the presence of two mechanisms in this catalytic reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Marc Strohmann, Andreas J. Vorholt, Walter Leitner
Summary: This study presents a method for transforming olefins into branched amines by combining hydroformylation/aldol condensation tandem reaction with reductive amination. The method utilizes a combined multiphase system that can be recycled 9 times. The study demonstrates the feasibility of the method and its potential applications in the production of surfactants.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Vladimir B. Kharitonov, Sofiya A. Runikhina, Yulia Nelyubina, Dmitry Muratov, Denis Chusov, Dmitry A. Loginov
Summary: A simple approach was developed to new effective rhodium catalysts for the construction of C-C and C-N bonds based on the 1,2,3,4-tetrahydrofluorenyl ligand. These catalysts showed efficient catalytic activity in various reactions, such as oxidative coupling of benzoic acids with alkynes and reductive amination of aldehydes and ketones, yielding high yields of the desired products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Organic
Valentin J. Geiger, Regina M. Oechsner, Paul H. Gehrtz, Ivana Fleischer
Summary: This review provides a summary of the recent methods for the synthesis of thioethers using homogeneous metals as catalysts. Due to the widespread presence of the thioether moiety in pharmaceutical, agricultural, and material applications, it is essential to develop new, efficient synthesis methods. Recent efforts have focused on the use of non-precious metal catalysts and the development of new bond-forming processes.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Physical
Vladimir B. Kharitonov, Dmitry V. Muratov, Yulia V. Nelyubina, Dmitry A. Loginov
Summary: This study demonstrated the influence of catalyst and alkyne nature on the regioselectivity of rhodium-catalyzed annulation of alkoxy-substituted benzoic acids. X-ray diffraction and DFT calculation data showed that the regioselectivity was determined by both steric and coordination effects of methoxy groups. The findings are believed to be applicable to other C-H activation reactions of methoxy-substituted arene compounds.
Article
Chemistry, Organic
Ryudai Michikita, Yoshinosuke Usuki, Tetsuya Satoh
Summary: A Rh(III)-catalyzed double C-H annulation of 3-(acetylamino)coumarins with internal arylacetylenes is reported, which selectively produces 8-aryl-6H- chromeno[4',3':4,5]pyrrolo[2,1-a]isoquinolin-6-ones accompanied by the formation of two C-C and two C-N bonds. This method also provides a straightforward route to natural product inspired pentacyclic pyrrolocoumarin derivatives from readily available building blocks.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Ariane Weber, Linus Porthun, Reinhard Schomaecker
Summary: The study investigated the homogeneously catalyzed reductive amination of long-chain aldehyde undecanal with diethylamine in an aqueous microemulsion system. The water-soluble rhodium/SulfoXantphos catalyst system was found suitable for this reaction, and the formation of alcohol by-product could be suppressed by using carbon monoxide. Reactant concentrations were identified as a critical factor for reaction performance, especially the initial concentration of the aldehyde which strongly impacted chemoselectivity due to equilibrium reactions.
Article
Chemistry, Organic
Hirotsugu Suzuki, Yumeng Liao, Yuya Kawai, Takanori Matsuda
Summary: The rhodium-catalyzed C(sp(2))-H ethoxycarbonylation reaction of indoles and arylpyridines using diethyl dicarbonate was developed. This catalytic process features an additive-free reaction with only ethanol and CO2 produced as byproducts, providing a CO-free and operationally simple protocol. The introduced ethoxycarbonyl group can be easily transformed into other ester and amide functionalities in a single step.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Wei-Chieh Chang, Helena Randel, Thomas Weyhermueller, Alexander A. A. Auer, Christophe Fares, Christophe Werle
Summary: In this study, a cooperative [Rh/P(O)nBu(2)] template was used for the catalytic hydrodefluorination (HDF) of perfluoroarenes under mild reaction conditions. The system showed high chemoselectivity and practicality, even in the presence of electron-donating functionalities and heterocycles. Mechanistic and theoretical studies identified a rhodium(I) dihydride complex as the catalytically relevant species and the crucial role of phosphine oxide as a cooperative fragment. Overall, this work demonstrates the potential of molecular templates for enhancing the reactivity in challenging bond activations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Martinez-Vivas, Macarena Poyatos, Eduardo Peris
Summary: H-1 NMR studies showed that a cationic complex with a pyridine-di-imidazolylidene pincer ligand exhibited high binding affinity with coronene in CH2Cl2. This binding was established through π-stacking interactions between coronene and the planar Rh-I complex. The interaction influenced the electron-donating strength of the pincer CNC ligand and increased the reaction rate of nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, as well as enhancing its catalytic activity in the cycloisomerization of 4-pentynoic acid. These findings highlight the significance of supramolecular interactions in modifying the reactivity and catalytic activity of square-planar metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Haoqiang Zhao, Jianbin Xu, Xin Xu, Yixiao Pan, Zexin Yu, Lijin Xu, Qinghua Fan, Patrick J. Walsh
Summary: The method employs inexpensive, readily available, and safe aryl carboxylic acids with a pyridine directing group to achieve C6-selective C-H arylation, allowing for a wide range of substituted 2-pyridones and affording products in yields of 41-91%.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Bo Li, Shihao Liu, Wu Fan, Xiaotong Shen, Jing Xu, Suhua Li
Summary: This work presents a rare example of Ir(I)-catalyzed direct decarbonylation of alpha-quaternary aldehydes, with a broad substrate scope and good functional group compatibility achieved through the careful selection of ligand. The alpha-chirality is preserved in this decarbonylation process. Additionally, a broad-spectrum decarbonylation of alpha-secondary and alpha-tertiary aldehydes containing multifunctional groups is achieved using an improved Rh(I)/DPPP recipe. Selective decarbonylation of alpha-tertiary aldehydes in the presence of alpha-quaternary ones is also demonstrated through the reactivity differences.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Kristina Zivkovic, Lilia M. Baldauf, Jessica L. Cryder, Alexa Villasenor, Valeria Reyes, Lauren E. Bernier, Theresa J. Thomas, Maxwell O'Toole, Kayleen Fulton, Curtis E. Moore, Arnold L. Rheingold, Christopher J. A. Daley
Summary: The study reports the first isolation and structural characterization of a series of chiral trinitrogen pincer ligands, as well as the methods for their preparation. Experimental results show that a novel microwave-based technique is more efficient, although currently not scalable.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Roushan Prakash Singh, Soumen Sinhababu, Neal P. Mankad
Summary: This Perspective reviews recent advances and applications of Al/M heterobimetallic catalysis in various areas, including polymerization, epoxide activation and carbonylation. The mechanistic role of the aluminum site is highlighted, and a comprehensive perspective is constructed by including a broad range of Al-containing metalloligands and Al/M combinations.
Article
Chemistry, Physical
Yoshimi Kato, Luqing Lin, Masahiro Kojima, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: By introducing pseudo-C2 symmetric tunable chiral carboxylic acids, the study achieved enantioselective C(sp(3))-H amidation reactions of substrates such as 2-alkylpyridines, improving the chiral selectivity towards the substrates.
