Article
Chemistry, Organic
Ruoqian Fan, Meiying Kuai, Dong Lin, Felix Bauer, Weiwei Fang
Summary: A new palladacyclic N-heterocyclic carbene pre-catalyst was designed and successfully applied for Pd-catalyzed C-N cross-coupling reactions of challenging heteroaryl chlorides. The desired aminated products were achieved in good to excellent yields.
Article
Chemistry, Physical
Tobias Gensch, Sleight R. Smith, Thomas J. Colacot, Yam N. Timsina, Guolin Xu, Ben W. Glasspoole, Matthew S. Sigman
Summary: In this study, we developed a tool set to aid the search for optimal catalysts and represented discrete ligands as continuous variables using the virtual library kraken. By using dimensionality reduction and clustering techniques, we proposed a Phosphine Optimization Screening Set (PHOSS) consisting of 32 commercially available ligands, which completely and evenly samples the chemical space. We demonstrated the application of this screening set in identifying active catalysts for different cross-coupling reactions and showed how evenly sampling the chemical space facilitates the identification of active catalysts.
Article
Chemistry, Physical
Archana Rajmane, Arjun Kumbhar
Summary: In recent years, Pd-catalyzed cross-coupling reactions have been widely used in various fields of chemistry. However, traditional phosphine ligands used in these reactions have limitations. Therefore, phosphine-free ligands and mixed donor P, N-ligands have attracted attention for their advantages in catalysis.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Andrea Monti, Raquel J. Rama, Beatriz Gomez, Celia Maya, Eleuterio Alvarez, Ernesto Carmona, M. Carmen Nicasio
Summary: The study presented the synthesis and characterization of neutral and cationic N-methyl- and N-phenyl-2-aminobiphenyl methanesulfonate palladacycles stabilized with dialkylterphenyl phosphines. By selecting different phosphine ligands, different coordination modes and structures of complexes were obtained. The most efficient precatalyst, [Pd(N-methyl-2-aminobiphenyl)L4](OMs), was identified for facilitating the coupling of aryl chlorides with secondary and primary amines and indoles.
INORGANICA CHIMICA ACTA
(2021)
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
Gen Li, Steven P. Miller, Alexander T. Radosevich
Summary: The reported method utilizes an organophosphorus catalyst and hydrosilane to drive the cross-selective intermolecular N-N reductive coupling of nitroarenes and anilines, with good chemoselectivity and functional group tolerance. Mechanistic investigations support an autotandem catalytic reaction cascade involving two sequential reduction events to produce the desired N-N bond.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Sabrina Kraeh, Iris Kachel, Oliver Trapp
Summary: Palladium-catalyzed cross-coupling reactions are efficient methods for organic synthesis, but heteroatom-containing compounds often complicate these reactions. This study introduces a highly active phosphine ligand that enables excellent yields in C-N coupling reactions at ambient temperature. The unique structure of the ligand, incorporating a silicon atom and a cyclohexane moiety, results in electron-rich properties. This ligand facilitates a broad range of coupling reactions under mild conditions in palladium catalysis.
Article
Multidisciplinary Sciences
Connor P. Delaney, Eva Lin, Qinan Huang, Isaac F. Yu, Guodong Rao, Lizhi Tao, Ana Jed, Serena M. Fantasia, Kurt A. Puentener, R. David Britt, John F. Hartwig
Summary: Copper complexes catalyze cross-coupling reactions through a newly discovered mechanism. The copper(II) complexes catalyze Ullmann coupling by synthesizing the C-O bond through concerted oxidative addition. This mechanism allows for high turnover numbers and the reactions can be performed in air.
Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Ryan Q. Tran, Long P. Dinh, Seth A. Jacoby, Nekoda W. Harris, William A. Swann, Savannah N. Williamson, Rebecca Y. Semsey, Larry Yet
Summary: 3-Aryl-1-phosphinoimidazo[1,5-a]pyridine ligands were synthesized through two different pathways using 2-aminomethylpyridine as the starting material, involving cyclization, iodination, and palladium-catalyzed cross-coupling phosphination reactions. These ligands were then evaluated in palladium-catalyzed sterically-hindered biaryl and heterobiaryl Suzuki-Miyaura cross-coupling reactions.
Article
Chemistry, Multidisciplinary
Justin Y. Wang, Kyoungmin Choi, Stephan J. Zuend, Kailaskumar Borate, Harish Shinde, Roland Goetz, John F. Hartwig
Summary: The study reports the Pd-catalyzed C-N coupling of hydrazine with (hetero)aryl chlorides and bromides to form aryl hydrazines with catalyst loadings as low as 100 ppm of Pd and KOH as base. Mechanistic studies revealed two catalyst resting states: an arylpalladium(II) hydroxide and arylpalladium(II) chloride, which interact in two interconnected catalytic cycles to produce the product. Kinetic studies showed that the coupling process occurs by rate-limiting deprotonation of a hydrazine-bound arylpalladium(II) chloride complex to give an arylpalladium(II) hydrazido complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Medicinal
Kohei Motojima, Abhijit Sen, Yoichi M. A. Yamada, Hiromasa Kaneko
Summary: Catalyst design using machine learning is important for reducing costs and development time in various industrial fields. This study focused on a reaction system involving Buchwald-Hartwig type cross-coupling (BHCC) and Suzuki-Miyaura type cross-coupling (SMCC) reactions. By constructing a machine-learning model considering all experimental conditions, the study aimed to accurately predict product yield for both BHCC and SMCC reactions and design catalysts that achieve target yield and develop novel reactions. Bayesian optimization was used with established variables to design new catalysts and improve reaction selectivity. Additionally, the catalyst design successfully introduced new reactions involving Cu, Rh, and Pt catalysts in a reaction system that previously only reacted with Ni or Pd transition metals.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Organic
Stephane Sengmany, Farah Daili, Ibtihal Kribii, Eric Leonel
Summary: Arylamines are a type of compounds commonly found in natural products and pharmaceuticals. Nickel-catalyzed amination of aryl halides is often used for their synthesis, but it requires complex and expensive nickel complexes. To address this issue, an electrochemical method based on sacrificial anode process is developed to generate a catalytic amount of nickel salts, enabling the amination of aryl halides under mild reaction conditions and providing access to a wide range of arylamines.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Binyang Jiang, Shi-Liang Shi
Summary: In this study, the first Pd-catalyzed aryl-alkyl cross-coupling of alkylzirconocenes and aryl halides was reported, with the critical role of a commercially available N-heterocyclic carbene (IPr) ligand for the palladium catalyst. This mild protocol tolerates various functional groups and heterocycles and is applicable to both terminal and internal alkenes.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
James M. Fordham, Philipp Kollmus, Monika Cavegn, Regina Schneider, Marco Santagostino
Summary: A screening method for rapid identification of catalytic conditions for Pd-catalyzed C-N cross-coupling reactions is presented. The method evaluates mixtures of precatalysts, ligands, and bases to identify productive conditions, and then optimizes them through deconvolution steps, uncovering the active catalyst and identifying the optimal solvent and base. The utility of this method is demonstrated through the identification of effective conditions for Pd-catalyzed cross-coupling of complex molecules, leading to the discovery of new chemical reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
