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, Multidisciplinary
Zi-Chao Wang, Pei-Pei Xie, Youjun Xu, Xin Hong, Shi-Liang Shi
Summary: The use of a bulky yet flexible chiral N-heterocyclic carbene (NHC) ligand in low-temperature Ni-catalyzed C-N cross-coupling has achieved high enantioselectivity with low barriers. Computational studies show that the rotations of multiple sigma-bonds on the chiral ligand can adapt to the changing needs of catalytic processes, making this design widely applicable to diverse transition states for challenging metal-catalyzed asymmetric cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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)
Article
Chemistry, Multidisciplinary
Peng Zhang, Qi Xu, Xiao-Mei Wang, Jia Feng, Chuan-Jun Lu, Yingzi Li, Ren-Rong Liu
Summary: The first enantioselective synthesis of N-N bisindole atropisomers via palladium-catalyzed construction of one indole skeleton is reported in this study. A wide variety of N-N axially chiral bisindoles were generated with good yields and excellent enantioselectivities through a cascade condensation/N-arylation reaction. The reaction mechanism and enantiocontrol were further investigated using density functional theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Guillermo Zaragoza, Lionel Delaude
Summary: The alkylation of caffeine with methyl iodide led to the synthesis of a new compound. Three complexes were obtained through multiple steps and were found to be highly active catalysts for the Suzuki-Miyaura cross-coupling reaction. The reaction showed high yields and could be carried out in a green solvent with low catalyst loading and in the presence of air.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shivhar B. Ambegave, Nitin T. Patil
Summary: This article provides an overview of the research progress in Au(I)/Au(III) catalysis, with a focus on cross-coupling reactions and 1,2-difunctionalization reactions of C-C multiple bonds. Understanding the reaction mechanisms is also highlighted as an important research direction.
Article
Chemistry, Physical
Lin-Yan Bao, Rong-Wan Gao, Shuang Wang, Run-Han Li, Bo Zhu, Zhong-Min Su, Wei Guan
Summary: Photoredox/transition-metal dual catalysis is an efficient method for constructing C-N bonds. However, low recovery, low utilization rate, and high cost have hindered its application and development. By utilizing zinc powder, the oxidation state of nickel was successfully regulated, achieving a catalytic cycle without light.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Wang Yao, Chuan-Jun Lu, Li-Wen Zhan, Yi Wu, Jia Feng, Ren-Rong Liu
Summary: In this study, a palladium-catalyzed enantioselective C-H activation method for pyrroles was reported, which successfully synthesized structurally diverse indole-pyrrole atropisomers with a chiral N-N axis, showing high yields and enantioselectivities. Furthermore, the kinetic resolution of trisubstituted N-N heterobiaryls with more sterically demanding substituents was also achieved. This versatile method enables the rapid and selective functionalization of pyrroles, facilitating the synthesis of valuable and complex N-N atropisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lin Liu, Kai-Xin Guo, Yu Tian, Chang-Jiang Yang, Qiang-Shuai Gu, Zhong-Liang Li, Liu Ye, Xin-Yuan Liu
Summary: The copper-catalyzed asymmetric cross-coupling of C(sp(3))-C(sp) bonds with terminal alkynes reported in this study shows high to excellent enantioselectivity. The rational design of chiral oxazoline-derived ligands is critical for success in tolerating oxidative conditions and inducing challenging enantiocontrol. This approach offers direct access to a variety of synthetically useful compounds and has great potential for the synthesis of enantioenriched medicinally relevant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Liyan Fu, Jingwen You, Yasushi Nishihara
Summary: This method utilizes a palladium catalyst to synthesize unsymmetrical biaryls by cross-coupling acyl chlorides with potassium perfluorobenzoates under redox-neutral conditions. Compared to traditional methods, this synthetic strategy allows for the easy preparation of reactants from inexpensive aromatic carboxylic acids.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Sushma Naharwal, Narendra Dinkar Kharat, Chikkagundagal K. Mahesha, Kiran Bajaj, Rajeev Sakhuja
Summary: Regioselective C-arylation and C,N-diarylation of 2-aryl-2,3-dihydrophthalazine-1,4-diones have been achieved successfully using diaryliodonium salts under base-mediated slightly modified Pd catalyzed conditions. These ligand-driven transformations afforded a wide range of diversely decorated bi(hetero)aryls in good-to-excellent yields, while N-arylated product can be obtained under similar Pd-catalyzed conditions in the absence of a ligand.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Jian-Hua Liu, Qing Zhou, Yao Lin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: In this study, a highly efficient atom-economic asymmetric alpha-allylation method using chiral-aldehyde/palladium catalyst was reported. This method enables the asymmetric alpha-allylation of different 1,3-dienes and allenes with N-unprotected amino acid esters, leading to the synthesis of alpha,alpha-disubstituted chiral alpha-amino acid esters with high efficiency, good yields, and stereoselectivities. No N-allylation byproducts were observed in these reactions. Two reaction models were proposed based on mechanistic control experiments. Overall, this work demonstrates a new approach for preparing structurally diverse chiral amino acids and provides insights for developing chiral-aldehyde catalytic systems.
Review
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Antoine de Gombert, Janette McKnight, Loic R. E. Pantaine, Michael C. Willis
Summary: This review focuses on the methods developed for the challenging coupling of 2-pyridine nucleophiles with (hetero)aryl electrophiles, ranging from traditional cross-coupling processes to alternative nucleophilic reagents and novel main group approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Pharmacology & Pharmacy
Adrian Sanchez, Carlos J. Carrasco, Francisco Montilla, Eleuterio Alvarez, Agustin Galindo, Maria Perez-Aranda, Eloisa Pajuelo, Ana Alcudia
Summary: In this study, a series of imidazole silver complexes with different alkyl groups were prepared and their antimicrobial properties were evaluated. The results showed that the antimicrobial activity of the complexes was related to their structure and the steric properties of the alkyl groups.
Article
Chemistry, Multidisciplinary
Tingxiang Yang, Abha Valavalkar, Antonio Romero-Arenas, Anindita Dasgupta, Patrick Then, Avinash Chettri, Christian Eggeling, Abel Ros, Uwe Pischel, Benjamin Dietzek-Ivansic
Summary: In this study, two four-coordinate organoboron N,C-chelate complexes with different functional terminals on the PEG chains were investigated for their photophysical properties in human MCF-7 cells. The excited-state relaxation dynamics were similar in DMSO, but aggregation was observed in water for the complexes with carboxylate terminal group. In cellulo studies showed different features depending on the nature of the anchoring PEG chains, with shorter lifetimes of charge-transfer state in cellulo compared to DMSO for complexes with an amino group.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Pilar Elias-Rodriguez, Esteban Matador, Manuel Benitez, Tomas Tejero, Elena Diez, Rosario Fernandez, Pedro Merino, David Monge, Jose M. Lassaletta
Summary: Modulable monosulfonyl squaramides activate gold(I) chloride complexes through H bonding in an intermolecular way. The combination of (PPh3)AuCl or IPrAuCl complexes with an optimal sulfonyl squaramide cocatalyst efficiently catalyzes various heterocyclizations and a cyclopropanation reaction. Computational studies reveal that the Au-Cl bond breaks through transligation to the triple bond in a ternary complex formed by the AuCl center dot center dot center dot HBD catalyst and the substrate.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Patricia Rodriguez-Salamanca, Gonzalo de Gonzalo, Jose A. Carmona, Joaquin Lopez-Serrano, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: This article describes a highly enantioselective biocatalytic dynamic kinetic resolution (DKR) for configurationally labile N-arylindole aldehydes. The DKR is achieved through atroposelective bioreduction of the carbonyl group using commercial ketoreductases (KREDs), resulting in axially chiral N-arylindole aminoalcohols with excellent conversions and optical purities. The strategy relies on the racemization of the stereogenic axis facilitated by a transient Lewis pair interaction between NMe2 and the aldehyde groups. This protocol offers a broad substrate scope under mild conditions.
Article
Chemistry, Physical
Pablo Vazquez-Dominguez, Antonio Romero-Arenas, Rosario Fernandez, Jose Maria Lassaletta, Abel Ros
Summary: The catalytic hydroarylation of alkynes is a useful method for synthesizing functionalized alkenes with excellent control of regio- and stereochemistry. However, there is a scarcity of asymmetric methodologies in this field. In this study, an atroposelective Ir-catalyzed C-H hydroarylation of alkynes was developed, enabling the asymmetric synthesis of axially chiral heterobiaryl trisubstituted olefins with high yields and enantioselectivities up to 98% ee.
Article
Chemistry, Multidisciplinary
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Pilar Elias Elias-Rodriguez, Esteban Matador, Manuel Benitez, Tomas Tejero, Elena Diez, Rosario Fernandez, Pedro Merino, David Monge, Jose M. Lassaletta
Summary: Modulable monosulfonyl squaramides activate gold(I) chloride complexes through H-bonding. Combinations of (PPh3)AuCl or IPrAuCl complexes and an optimal sulfonyl squaramide cocatalyst efficiently catalyze heterocyclizations and a cyclopropanation reaction, while avoiding undesired side reactions. Computational studies suggest that the Au-Cl bond breaks by transligation to the triple bond in a ternary complex formed by the AuCl...HBD catalyst and the substrate.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Carlos J. Carrasco, Francisco Montilla, Eleuterio Alvarez, Agustin Galindo, Maria Perez-Aranda, Eloisa Pajuelo, Ana Alcudia
Summary: In this study, novel one-dimensional or two-dimensional coordination polymers were synthesized and their antimicrobial properties were evaluated. The results showed that complexes 2a and 2b' exhibited the best antimicrobial activity against the tested pathogens.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
