Review
Chemistry, Applied
Oleg Y. Lyakin, Dmitry S. Bushmin, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: This review summarizes the recent advances in homogeneous oxidation of hydrocarbon C(sp(3))-H bonds catalyzed by nickel and palladium complexes, and discusses the correlations between the catalyst structure, ligand properties, catalytic conditions, and catalytic reactivity (efficiency, chemoselectivity, and regioselectivity).
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nurbey Gulia, Jaroslaw Fornalski, Adrianna Gumienna, Malgorzata Ambroziak, Slawomir Szafert
Summary: This study reports a method of palladium-catalyzed C-H arylation assisted with a 3,4,4-trimethylpyrazol-5-on directing group, which selectively provides mono- and di-ortho-arylated products. The steric hindrance between the directing group and the already introduced aryl substituent enables control of mono- vs. diarylation selectivity by the reaction temperature. A series of monosubstituted and disubstituted derivatives were obtained in good yields. In addition, a one-pot procedure for unsymmetrical double-arylation to give corresponding products was developed, and the synthesis and X-ray study of intermediate palladium metallacycles were conducted. The decarboxylative cleavage of the pyrazolone directing group under mild conditions gave synthetically useful hydrazones. Overall, this solution provides an alternative synthetic pathway for ortho arylated derivatives of arylhydrazines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Alexandra M. Zima, Oleg Y. Lyakin, Anna A. Bryliakova, Dmitrii E. Babushkin, Konstantin P. Bryliakov, Evgenii P. Talsi
Summary: Catalytic approaches to late-stage creation of new C-O bonds, especially via oxygenation of particular C-H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established. In this Personal Account, recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp(3))-H groups are analyzed, with a focus on the factors governing the oxidation chemo- and stereoselectivity.
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, Multidisciplinary
Rie Yoshimoto, Attila Taborosi, Qiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori
Summary: The reaction between aromatic amides and maleimides, catalyzed by palladium, leads to the formation of a product with double C-H bond activation, occurring at both the benzylic and meta positions. Computational chemistry studies reveal a stepwise mechanism involving a six-membered palladacycle, maleimide insertion, protonation of the Pd-N bond, and activation of the meta C-H bond. The site selectivity is determined by the interaction energy controlling the insertion of maleimide into the Pd-C(sp(3)) bond. The meta C-H bond activation step is identified as the rate-determining step based on the energetic span model. The 2-thiomethylphenyl group is found to function effectively as a directing group due to strong Pd-S bonding and the destabilizing effect of the deformation energy.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Rui Liu, Meng-Lan Shen, Lian-Feng Fan, Xiao-Le Zhou, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Allylamines are important for synthesizing bioactive compounds and can be obtained through the palladium-catalyzed allylic C-H amination of 1,4-dienes. This reaction favors the formation of thermodynamically unstable Z-allylamines with aromatic amines. Aliphatic cyclic amines can also participate, but linear dienyl allylic amines are the main products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Nahiane Pipaon Fernandez, Gregory Gaube, Kyla J. Woelk, Mathias Burns, Damian P. Hruszkewycz, David C. Leitch
Summary: We present a new method for direct C-C bond formation using tandem C-O/C-H activation mediated by palladium catalyst. This approach allows for base-free direct C-H alkenylation by combining C-O oxidative addition at enol pivalates and concerted metalation-deprotonation of functionalized heterocycles. Mechanistic studies show that C-O oxidative addition is reversible and C-H activation occurs directly from the Pd(II) C-O oxidative addition product. In situ P-31 NMR spectroscopy reveals that (Cy3P)(2)Pd-(alkenyl)(OPiv) species is the predominant catalyst resting state during the reactions.
Article
Chemistry, Multidisciplinary
Nihad Salameh, Federica Valentini, Olivier Baudoin, Luigi Vaccaro
Summary: We report a general and efficient enantioselective C-H arylation of aryl bromides using BozPhos as the bisphosphine ligand and SP-NHC-PdII as recoverable heterogeneous catalyst. By exploiting the release and catch mechanism of action, high enantioselectivities were achieved across different substrates containing methyl, cyclopropyl and aryl C-H bonds. The developed catalytic system provides a more sustainable solution for the synthesis of high added-value chiral products through recycling of the precious metal.
Review
Environmental Sciences
Govardhana Reddy Peddiahgari Vasu, Krishna Reddy Motakatla Venkata, Raghava Reddy Kakarla, Kalluri V. S. Ranganath, Tejraj M. Aminabhavi
Summary: This article explores the research of Pd-PEPPSI complexes in recent years, introducing the synthesis of these catalysts and their applications in various reactions. The article also discusses the reusable heterogeneous PdPEPPSI complexes and their catalytic applications, and concludes with a discussion on chiral Pd complexes and their asymmetric transformations.
ENVIRONMENTAL RESEARCH
(2023)
Article
Chemistry, Physical
Igor Beckers, Besir Krasniqi, Prashant Kumar, Daniel Escudero, Dirk De Vos
Summary: Two indoles linked by a C-C bond have emerged as promising scaffolds in medicinal chemistry. In this study, selective C-H/C-H cross-coupling of N-substituted indoles without directing groups was achieved under mild conditions, driven by molecular oxygen. The ligand-controlled selectivity can be exploited to achieve selective cross-coupling between two indoles with different substitution patterns.
Article
Chemistry, Multidisciplinary
Francesco Ferlin, Ioannis Anastasiou, Nihad Salameh, Takeru Miyakoshi, Olivier Baudoin, Luigi Vaccaro
Summary: A heterogeneous catalyst has been prepared for the intramolecular activation/cyclization reaction to synthesize indolines. The catalyst showed high efficiency through a release and catch mechanism, facilitated by iodide ligands. The heterogeneous nature of the catalyst was further utilized in the design of a continuous-flow protocol, enabling efficient recovery and reuse.
Article
Chemistry, Multidisciplinary
Kristina Plevova, Peter Kisszekelyi, Denisa Vargova, Samuel Andrejcak, Viktor Toth, LukaS Fertal, Erik Rakovsky, Juraj Filo, Radovan Sebesta
Summary: This study demonstrates the diastereoselective double C-H heteroarylation of chiral ferrocenes using Pd-complexes with chiral mono-protected amino acids, resulting in a variety of functionalized compounds. The absolute configurations of CH-activation products were confirmed using X-ray crystallographic analysis and CD spectroscopy, while insights into the reaction mechanism and stereoinduction were provided by F-19 NMR kinetic study and DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Caroline Berrou, Sebastien Prevost
Summary: This study describes a direct C8-oxygenation of naphthalene derivatives using different carbonyl groups as directing groups in a palladium-catalyzed oxidation reaction with PhI(OAc)(2) in a TFA/TFAA mixture. Interestingly, the use of Weinreb amide as the directing group results in the direct formation of naphtholactone skeleton. This methodology has been successfully applied to the synthesis of variously substituted naphtholactones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Monak Patel, Bhargav Desai, Arti Ramani, Bharatkumar Z. Dholakiya, Togati Naveen
Summary: This review focuses on recent developments in the synthesis of various carbo- and heterocyclic compounds via palladium catalyzed/norbornene mediated cascade processes triggered by ortho C-H alkylation, amination or arylation of aryl iodides, covering literature from 2010-2021.
Article
Chemistry, Organic
Rita Ferro, Nuno Viduedo, A. Sofia Santos, Artur M. S. Silva, Beatriz Royo, M. Manuel B. Marques
Summary: A bimetallic synthesis method for 2-arylindoles from alcohols and anilines is presented, involving the dehydrogenation or oxidation of secondary alcohols using Ni or Mn catalysts, followed by conversion of the formed ketone into an imine intermediate and subsequent Pd-catalyzed oxidative cyclization to obtain the desired 2-arylindole. The intermediates generated were not isolated, allowing for the preparation of a series of 2-arylindoles. The compatibility of catalysts was explored, and the optimized protocol enables the integration of Earth-abundant metals and palladium complexes, enhancing the sustainability of N-heterocycle synthesis.
SYNTHESIS-STUTTGART
(2023)
