Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Physical
Sanita B. Tailor, Mattia Manzotti, Gavin J. Smith, Sean A. Davis, Robin B. Bedford
Summary: The cobalt-catalyzed Suzuki biaryl cross-coupling reaction using alkoxide bases, with strict stoichiometric control and selection of the right boron ester, is shown to be achievable. Excessive alkoxide bases or lithium additives can inhibit or poison the catalyst, while a neopentane diol-based boron ester is crucial for optimal performance.Mechanistic and computational studies have been carried out to investigate the reaction mechanism and explain unexpected observations.
Article
Chemistry, Organic
Regina M. Oechsner, Ivo H. Lindenmaier, Ivana Fleischer
Summary: We present a nickel catalyzed C-S cross-coupling reaction of aryl and alkenyl triflates with alkyl thiols. By using an air-stable nickel precatalyst, various thioethers could be synthesized under mild reaction conditions within a short reaction time. The reaction demonstrated a broad substrate scope, including pharmaceutically relevant compounds.
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Raj Laxmi, Ravi Prakash Behere, Arunava Manna, Biplab Kumar Kuila
Summary: A reusable polymer-embedded Pd nanoparticle dip-catalyst membrane was developed to meet the criteria for a successful catalyst, including simple fabrication, high efficiency, stability, flexibility, straightforward recovery, reusability, and ease of scale-up. This membrane achieved high yields in various C-C bond formation reactions and moderate to good yields in C-X bond formations under mild reaction conditions. The system demonstrated stability, no significant leaching of Pd, and functional group tolerance.
NEW JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Ramagonolla Kranthikumar
Summary: The formation of new C-C bonds at sp3-hybridized centers is a significant research area that opens up unexplored chemical space, addresses the challenge of forming stereocontrolled C-C bonds, and enables rapid synthesis of C(sp3)-rich drug molecules. The recent advancements in nickel catalysis in this field are particularly attractive.
Article
Chemistry, Organic
Yi-Bing Yin, Xiao-Shui Peng, Henry N. C. Wong
Summary: A one-pot iron-catalyzed cross-coupling protocol was developed for the synthesis of unsymmetrical biaryls using aryl chlorides, aryl bromides, and magnesium metal. The key step in this reaction is the in situ generation of Grignard reagents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Applied
Sara Payamifar, Foad Kazemi, Babak Kaboudin
Summary: This study introduced a convenient nickel-catalyzed protocol for the Suzuki-Miyaura coupling reaction using a simple mixture of Ni(II) and unfunctionalized beta-cyclodextrin in water. The environmentally friendly and cost-efficient method allows the synthesis of biaryls from arylboronic acids and various aryl halides. The catalyst can be recycled for multiple runs with only a small decrease in catalytic activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jinpeng Li, Changyu Huang, Daheng Wen, Qingshu Zheng, Bo Tu, Tao Tu
Summary: A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been successfully achieved under mild conditions. The protocol offers a broad substrate scope with excellent functional group tolerance at a low catalyst loading, making it powerful for synthesizing various aromatic amines. Selective coupling of aryl chlorides to the amino fragments of amides rather than the carbonyl moieties expands the usage of inactive amides.
Article
Chemistry, Multidisciplinary
Muhammad Asif Iqbal, Le Lu, Hina Mehmood, Ruimao Hua
Summary: This study reports a Cs2CO3-promoted cross-coupling reaction of arenes with cyano-/nitro-substituted aryl halides in DMSO to afford biaryls in the absence of ligands. The cyano/nitro groups in biaryls are shown to be useful for further transformations. Additionally, the formation of dibenzofurans from reactions between arenes and 1-bromo-2-iodobenzene is reported. A radical mechanism for the formation of biaryls is proposed based on control experiments and theoretical studies.
Article
Chemistry, Organic
Qianqian Lu, Haixing Guan, Yan-En Wang, Dan Xiong, Tingzhi Lin, Fei Xue, Jianyou Mao
Summary: A visible-light-promoted nickel/photoredox-catalyzed reductive cross-coupling reaction between vinyl bromides and benzyl chlorides has been reported, enabling the synthesis of a diverse array of enantioenriched allylic centers in good yields and high enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Giorgio Rizzo, Gianluigi Albano, Teresa Sibillano, Cinzia Giannini, Roberta Musio, Fiorenzo G. Omenetto, Gianluca M. Farinola
Summary: This paper reports the application of a silk fibroin-supported Palladium catalyst (Pd/SF) in Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides. The existence of catalytic pockets where monoatomic palladium species can form stable complexes with SF is hypothesized and supported by experimental analysis. The size of the catalytic pocket of Pd/SF is estimated to be approximately 15 angstroms using computational modeling.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiaomin Shu, De Zhong, Yanmei Lin, Xiao Qin, Haohua Huo
Summary: We report a general and modular approach for the direct enantioselective alpha-arylation of saturated azacycles and acyclic N-alkyl benzamides via nickel/photoredox dual catalysis. This method requires no oxidants or organometallic reagents, features broad substrate scope and high enantioselectivities, and is applicable to late-stage diversification of medicinally relevant complex molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Wei Sun, Luke Wilding-Steele, Richard C. D. Brown, David C. C. Harrowven
Summary: Benzyloxy iodobenzene ethers can undergo cyclisation to form benzo[c]chromenes under UVC irradiation without the need for reagents or catalysts. The reactions proceed through the generation of triplet aryl cations, 5-exo and 3-exo-cyclisations, and subsequent rearomatisation. This methodology is versatile, convenient, and applicable to various related ring systems.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Beatrice Lansbergen, Paola Granatino, Tobias Ritter
Summary: In this study, an undirected para-selective two-step C-H alkylation method for complex arenes useful for late-stage functionalization is presented. By combining site-selective C-H thianthrenation with palladium-catalyzed reductive electrophile cross-coupling, a diverse range of synthetically useful alkylated arenes can be accessed with high selectivity and practicality. The robustness of this transformation is further demonstrated by thianthrenium-based reductive coupling of two complex fragments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)