Article
Chemistry, Multidisciplinary
Jingjie Yang, Zhuofan Gui, Yuli He, Shaolin Zhu
Summary: An attractive approach for selective functionalization of remote C-H bonds is the metal/hydride shift/cross-coupling reaction sequence. In this study, an unprecedented aryl-to-vinyl 1,4-nickel/hydride shift reaction is reported, which selectively traps migratory alkenylnickel species generated in situ by various coupling partners to access trisubstituted alkenes with excellent regio- and stereoselectivity. Unlike previously reported ipso-aryl coupling reactions, this strategy provides remote alkenyl C-H functionalized products with high yield and excellent chemo-, regio-, and E/Z-selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Stavros K. Kariofillis, Abigail G. Doyle
Summary: In recent years, the development of light-driven reactions has made significant advancements in synthetic organic chemistry, particularly in combining photoredox and nickel catalysis for challenging cross-coupling reactions. The question of whether photo-induced activation of the nickel catalyst itself could lead to new approaches to cross-coupling has been explored. By utilizing a visible-light-driven mechanism for chlorine radical formation and conducting mechanistic investigations on organometallic Ni complexes relevant to cross-coupling, the study aims to facilitate new catalyst design and develop novel synthetic methods.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Physical
Mo Chen, John Montgomery
Summary: Regio- and enantioselective functionalization of heteroarene C-H bonds in the absence of directing groups has been a long-standing challenge. In this study, we developed a new approach for intermolecular enantioselective C-H alkylation of heteroarenes using nickel catalysts. The reaction can be carried out under mild conditions without the need for Lewis acid co-catalysts. Synthesis of NHC nickel complexes stabilized with 1,5-hexadiene improved the functional group tolerance and heteroarene scope. Mechanistic investigations revealed a ligand-to-ligand hydrogen transfer pathway.
Article
Chemistry, Physical
Nicholas S. D. Solomon, Mohan Bhadbhade, Ruoming Tian, Sinead T. Keaveney
Summary: Due to the prevalence of the trifluoromethyl group (CF3) in high-value organic compounds, there is a constant demand for more selective, efficient and economical trifluoromethylation strategies. In this report, the use of cheap and atom economical CF3I in transition metal catalyzed trifluoromethylation is investigated experimentally and computationally. Novel C-H trifluoromethylation processes using both palladium and nickel catalysis are developed. The methodology is remarkably selective and can tolerate various substituents.
Article
Chemistry, Physical
Chen-Hsun Hung, Ting-Hsuan Wang, Glenn P. A. Yap, Joon Ching Juan, Tiow-Gan Ong
Summary: This study presents a Ni-catalyzed heteroarene C-H/arenol C-OH coupling reaction without the need for strong Lewis-acid additive and low atom-economy protecting reagent. A range of arenols and heteroarenes can be effectively catalyzed using an in-situ activating reagent of pivalic anhydride. Mechanistic studies and identification of intermediates have been conducted to understand the nature of the catalytic reactions.
Article
Chemistry, Multidisciplinary
Soosan Hosseinmardi, Andreas Scheurer, Frank W. Heinemann, Nicola Marigo, Dominik Munz, Karsten Meyer
Summary: This study reports a two-step protonation reaction from a Ni-0 precursor to dihydrogen, with the formation of a rare nickel dihydrogen complex in the second protonation step.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Xiantang Li, Yujia Mao, Pei Fan, Chuan Wang
Summary: We have developed a nickel/TBADT cocatalyzed acyl C-H benzylation method, which allows for the synthesis of various ketones under mild reaction conditions. This protocol provides a convenient and efficient approach in synthetic chemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Supriya Rej, Naoto Chatani
Summary: Considerable advances have been made in the field of C-H functionalization, with special interest in C-H borylation due to its wide applications. Transition-metal-catalyzed regioselective strategies have been developed, but the use of precious metals and contamination by metal precursors limit their application in large-scale synthesis. Recent trends involve the use of transition-metal-free systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Lukas Kletsch, Rose Jordan, Alicia S. Koecher, Stefan Buss, Cristian A. Strassert, Axel Klein
Summary: The three complexes containing the tridentate ligand were synthesised using a base-assisted C-H activation method. Cyclic voltammetry showed increasing oxidation potentials along the series, while DFT calculations confirmed the character of molecular orbitals and contributions from various orbitals in the complexes. UV-vis absorption band energies also increased along the series, with different metal-to-ligand charge transfer properties observed.
Article
Chemistry, Physical
Shidheshwar B. Ankade, Pragnya Paramita Samal, Vineeta Soni, Rajesh G. Gonnade, Sailaja Krishnamurty, Benudhar Punji
Summary: The intramolecular oxidative cyclization of indoles via nickel-catalyzed C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/C(sp(2))-H couplings provides access to biologically relevant five- and six-membered substituted cyclopentaindolones, carbazolones, and indenoindolones in high yields. The mechanism involves a Ni(II)/Ni(III) pathway without the participation of a carbon-based radical.
Article
Chemistry, Multidisciplinary
Guangrong Meng, Liang Hu, Martin Tomanik, Jin-Quan Yu
Summary: Pd-II-catalyzed beta- and gamma-C(sp(3))-H heteroarylation of free carboxylic acids using pyridine-pyridone ligands overcomes limitations in selective functionalization and compatibility with heteroatoms. A sequence of three consecutive C(sp(3))-H activation reactions of pivalic acid constructs diverse quaternary carbon centers containing heteroaryls, offering a valuable tool for breaking new ground in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Santosh Kumar Keshri, Suchithra Madhavan, Manmohan Kapur
Summary: Transition-metal catalysis has revolutionized organic synthesis by enabling efficient C-C and C-heteroatom bond formation. To functionalize nonbiased C-H bonds, various strategies have been developed, including the use of directing groups and substrate modification.
Article
Chemistry, Organic
Uros Todorovic, Immo Klose, Nuno Maulide
Summary: Thiocyanates, a versatile building block in organic synthesis, can be easily accessed through an interrupted Pummerer reaction of sulfoxides. This dealkylative functionalization can proceed under mild conditions by electrophilic activation of the sulfoxide partner, and the resulting thiocyanate can be used as a handle for diversification in a straightforward one-pot procedure.
Article
Chemistry, Organic
Hee Chan Noh, Cheol-Eui Kim, Kyungsup Lee, Dongwook Kim, Phil Ho Lee
Summary: A regioselective B(4)-alkenylation method has been developed using o-carboranyl sulfoxonium ylides and alkynes through B(4)-H activation catalyzed by Iridium(I). Sequential B(4)- and B(6)-alkenylation reactions resulted in the synthesis of B(3,5)-dialkenylated o-carboranyl sulfoxonium ylides in one pot. This method allows the introduction of two alkenyl groups at positions 3 and 5 of the carborane, with the sulfoxonium ylide serving as a directing group that can be further functionalized to B-alkenylated o-carboranyl trichloromethyl ketones.
Review
Chemistry, Organic
Phuc H. Pham, Haley A. Petersen, Jaclyn L. Katsirubas, Oana R. Luca
Summary: This paper summarizes recent advances in mediated electrochemical and photoelectrochemical bond activation, including C-H, C-C, C-N, and other C-heteroatom bonds, driven by a resurgence of interest in electrode-driven synthetic methods.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
