Article
Chemistry, Multidisciplinary
Sif T. Linde, Vasco Corti, Vibeke H. Lauridsen, Johannes N. Lamhauge, Karl Anker Jorgensen, Nomaan M. Rezayee
Summary: This article presents a method for obtaining a versatile chiral biaryl structure through C-H halogenation reactions using high-valent Pd catalysis and chiral transient directing groups. The method is scalable, moisture and air insensitive, and in some cases, requires low Pd-loadings of only 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls can be prepared in high yield and excellent stereoselectivity, serving as building blocks for various reactions with orthogonal synthetic handles.
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
Princi Gupta, Suchithra Madhavan, Manmohan Kapur
Summary: In this study, a method for distal C-H functionalization of monosubstituted ferrocenes using an easily removable directing group under a Pd-II/ mono-N-protected amino-acid ligand catalytic system is reported. The synthetic protocol allows for the synthesis of ferrocene 1,3-derivatives with broad scope in olefins, by functionalizing ferrocenyl methylamine in moderate to good yields through a highly strained ferrocene appended 12-membered palladacycle intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Luo-Yan Liu, Zhoulong Fan, Md Emdadul Hoque, Shaoqun Qian, Guangrong Meng, Nikita Chekshin, Keita Tanaka, Jennifer X. X. Qiao, Kap-Sun Yeung, Jin-Quan Yu
Summary: Remote C-H functionalization of heterocyclic biaryls is crucial in synthesis and medicinal chemistry. New catalytic templates have been developed to functionalize the hindered ortho-C-H bonds of heterobiaryls, using directing heteroatom at the meta- or para-positions, with unprecedented site-selectivity. This protocol overcomes steric and electronic effects, allowing olefination of sterically hindered heterobiaryls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Physical
Guoshuai Li, Yifei Yan, Pengfei Zhang, Xiaohua Xu, Zhong Jin
Summary: A new palladium-catalyzed meta-selective C-H olefination of aromatic carbonyl compounds was achieved by utilizing noncovalent hydrogen-bonding interaction directed by engineered N,N'-substituted ureas, demonstrating site-selective control without the need for prior stoichiometric installation and removal of directing groups.
Article
Chemistry, Applied
Takahiro Yamada, Kosaku Tanaka, Yoshimitsu Hashimoto, Nobuyoshi Morita, Osamu Tamura
Summary: Here, the authors describe a reaction system based on Pd(II) catalyst and Tl(OCOCF3)3 for the electrophilic C3-H alkenylation of 2,6-dialkoxypyridines with alkenes. The synergistic action of the Pd/thioether ligand catalytic system and Tl(III) enables efficient C-H alkenylation of various nitrogen heteroaromatics with complete regioselectivity. Mechanistic studies suggest that the reaction proceeds via electrophilic thallation of heteroarenes followed by Pd-catalyzed Heck-type reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Hang Wang, Huiling Li, Xiahe Chen, Chunlin Zhou, Shangda Li, Yun-Fang Yang, Gang Li
Summary: In this study, a chiral ligand-controlled, asymmetric remote meta-C-H activation method was reported. By using a specific chiral ligand and Pd(II) catalyst, asymmetric C-H olefination and arylation of arenes were achieved. The origins of enantioselectivity were explained through density functional theory calculations.
Article
Chemistry, Multidisciplinary
Zhiqian Yu, Qianhui Liu, Qian Li, Zhenmei Huang, Yudong Yang, Jingsong You
Summary: In this study, we present a new approach allowing remote editing of stacked aromatic assemblies through the use of a transient ligand as a bridge. Our results demonstrate the successful heteroannular C-H functionalization and uncover a unique reaction mechanism involving olefin coordination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Hang Wang, Huiling Li, Xiahe Chen, Chunlin Zhou, Shangda Li, Yun-Fang Yang, Gang Li
Summary: The use of a chiral ligand-controlled, asymmetric remote meta-C-H activation enables asymmetric C-H olefination and arylation of hydrocinnamic acid derivatives. The origins of the enantioselectivity were explained using density functional theory calculations.
Article
Chemistry, Applied
Francisco Villalba, Ana C. Albeniz
Summary: The pyridone fragment in the ligand plays a crucial role in the C-H activation step of the oxidative Heck reaction. The presence of bipy-6-OH is required for the alkenylation of low acidity fluoroarenes, while it is detrimental for high acidity fluoroarenes. The use of catalytic amount of sodium molybdate as a base is optimal in all these reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Article
Chemistry, Multidisciplinary
Yasushi Obora, Yuka Anno, Ryuhei Okamoto, Toyomi Matsu-ura, Yasutaka Ishii
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2011)
Article
Chemistry, Multidisciplinary
Kenichiro Kamae, Yasushi Obora, Yasutaka Ishii
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2009)
Article
Chemistry, Multidisciplinary
Nobuyuki Yamamoto, Yasushi Obora, Yasutaka Ishii
Article
Chemistry, Multidisciplinary
Shintaro Hatanaka, Yasushi Obora, Yasutaka Ishii
CHEMISTRY-A EUROPEAN JOURNAL
(2010)
Article
Chemistry, Organic
Yosuke Iuchi, Megumi Hyotanishi, Brittany E. Miller, Kensaku Maeda, Yasushi Obora, Yasutaka Ishii
JOURNAL OF ORGANIC CHEMISTRY
(2010)
Article
Chemistry, Organic
Yasushi Obora, Yasushi Satoh, Yasutaka Ishii
JOURNAL OF ORGANIC CHEMISTRY
(2010)
Article
Chemistry, Organic
Nobuyuki Yamamoto, Yasushi Obora, Yasutaka Ishii
JOURNAL OF ORGANIC CHEMISTRY
(2011)
Article
Chemistry, Inorganic & Nuclear
Makoto Ozaki, Yasushi Obora, Yusuke Tada, Yasutaka Ishii
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2013)
Article
Chemistry, Multidisciplinary
Yosuke Iuchi, Yasushi Obora, Yasutaka Ishii
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2010)
Review
Biochemistry & Molecular Biology
Yasushi Obora, Yasutaka Ishii
Article
Chemistry, Organic
Yasushi Obora, Yoshihisa Okabe, Yasutaka Ishii
ORGANIC & BIOMOLECULAR CHEMISTRY
(2010)
Article
Chemistry, Organic
Yasushi Obora, Yasutaka Ishii
Article
Chemistry, Organic
Norihide Horikawa, Yasushi Obora, Yasutaka Ishii
Review
Chemistry, Physical
Yasushi Obora, Yasutaka Ishii
