Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mixiang Tian, Lidong Shao, Xiaosan Su, Xuhong Zhou, Honglei Zhang, Kun Wei, Ruifen Sun, Junliang Wang
Summary: A new method has been developed for selective oxygenation of benzaldehydes and benzylic amines at the ortho positions to prepare fluoroalkyl aryl ethers.
Article
Chemistry, Multidisciplinary
Nanxing Gao, Yanshun Li, Guorui Cao, Dawei Teng
Summary: The cross-electrophile coupling of aryl bromides and cyclic secondary alkyl bromides catalyzed by nickel/spiro-bidentate-pyox ligands with lithium chloride as the additive for Csp(2)-Csp(3) bond formation was reported. Various aryl-cyclic secondary alkyl Csp(2)-Csp(3) bond products were successfully synthesized under optimal reaction conditions.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Sunit Hazra, Koji Hirano, Masahiro Miura
Summary: A novel method for C4-selective C-H alkenylation of 3-carboxy-2-pyridones with styrenes has been developed using a rhodium catalyst. The carboxylic group at the C3 position plays a key role in directing the C4 alkenylation of the products with concomitant decarboxylation. The exclusive C4 selectivity is observed even in the presence of potentially more reactive C-H bonds, allowing for the preparation of multiply substituted 2-pyridones via sequential C-H functionalization reactions.
Article
Chemistry, Organic
Yangyang Wang, Gaorong Wu, Xiaobo Xu, Binghan Pang, Shaowen Liao, Yafei Ji
Summary: This study develops a method for the direct arylation of aliphatic ketones via Pd-catalyzed beta-C(sp(3))-H bond functionalization using 2-(aminooxy)-N,N-dimethylacetamide as a novel transient directing group (TDG), resulting in moderate to good yields. The reaction is tolerant to abundant substrate of ketones and aryl iodides, expanding the applications of TDGs.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Chou-Yi Hsu, Ahmed Kareem Obaid Aldulaimi, Mustafa Humam Sami, Hala Bahir, Ayat Hussein Adhab, Shelesh Krishna Saraswat
Summary: In recent years, the direct hydrazinosulfonylation of aryl electrophiles with SO2 and hydrazines has become a highly efficient and versatile method for synthesizing aryl N-aminosulfonamides. This review article aims to summarize the literature on the preparation of aryl N-aminosulfonamides through this method, with a focus on the mechanistic features of the reactions. It can serve as a guide for chemists and inspire future research on this topic.
Article
Chemistry, Physical
Philip A. Provencher, Katherine L. Bay, John F. Hoskin, K. N. Houk, Jin-Quan Yu, Erik J. Sorensen
Summary: This study presents a Pd(II)-catalyzed method for cyclative C(sp(3))-H arylation of ketones, utilizing a transient directing group. By carefully selecting reaction conditions and the directing group, the researchers were able to enhance selectivity and yield, facilitating the arylation reaction to occur.
Article
Chemistry, Organic
Lei Yang, Xinchao Wang, Meng Zhang, Shangda Li, Xinqiang Fang, Gang Li
Summary: This study reports a Pd-catalyzed remote isodesmic meta-C-H iodination of phenethylamines, benzylamines, and 2-aryl anilines using 1-iodo-4-methoxy-2-nitrobenzene as the mild iodinating reagent. A range of valuable meta-iodinated and even multi-halogenated amines were successfully synthesized, paving the way for synthetic chemists to access various amine derivatives at the challenging meta-positions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Min Zhang, Zhangyi Fu, Anping Luo, Xingwen Pu, Menglei Wang, Ying Huang, Yudong Yang, Jingsong You
Summary: The study presents a concise route for site-selective arylation of polycyclic aromatic hydrocarbons with easily available aryl sources, contributing to the bottom-up preparation of pi-extended PAHs. Additionally, a C8-H annulation protocol has been developed to rapidly assemble benzanthrones by simply switching the solvent to 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP).
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Multidisciplinary
Jayabrata Das, Wajid Ali, Debabrata Maiti
Summary: In this review, the development of C(sp3)-H activation is highlighted, including its origins, progression, and overcoming of limitations, to identify future research directions. The three main strategies for C(sp3)-H activation in aliphatic molecules are static directing group (DG) or template-assisted approach, transient DG (TDG) approach, and native functional group (NFG)-assisted approach. Each section provides a brief discussion on the evolution, functionalization type, advantages, and shortcomings of C(sp3)-H activation.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Multidisciplinary
Lincong Sun, Yuyao Zhao, Bingxian Liu, Junbiao Chang, Xingwei Li
Summary: The rhodium-catalyzed tandem twofold C-H bond activation reactions of para-olefin-tethered arenes have been achieved, leading to the synthesis of diverse 2,3-dihydrobenzofuran platforms. The reaction proceeds through the activation of ortho-C-H bonds in the arene and sequential activation of meta-C-H bonds, resulting in C-C or N-C difunctionalization.
Article
Chemistry, Inorganic & Nuclear
Hector Torralvo, Joan Albert, Xavier Ariza, Merce Font-Bardia, Jordi Garcia, Jaume Granell, Manuel Martinez
Summary: The study demonstrated the significant impact of specific structures on the C-H activation reactions of imines related to 2-pyridinecarboxaldehyde catalyzed by Pd(II) and Pt(II) compounds, with Pt(II) centers being more reactive. The nature of the metal center and the kinetics mechanistic studies have been shown to play a crucial role in the overall process.
Article
Chemistry, Organic
Kiran Matcha, Konstantin Chernichenko, Kevin Jouvin, Suresh Babu Guduguntla, Duc N. Tran, Stephen Bell, Warren Paden, Marek Figlus, Colin Muir, Alain Elliott, Cristina Hernandez Diaz
Summary: A palladium-catalyzed Heck reaction between 2-oxyacrylates and aryl bromides has been successfully developed, using DavePhos as an efficient ligand. The resulting 2oxycinnamates serve as valuable precursors, providing synthetically useful monoaryl pyruvates or ortho ester-protected monoaryl pyruvates, depending on the nature of the 2-oxy group. The formation of such ortho esters via alkoxide addition is novel, and a plausible mechanism with an oxyallyl zwitterion as the key intermediate has been identified through computational studies.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mei-Ling Wang, Hui Xu, Han-Yuan Li, Biao Ma, Zhen-Yu Wang, Xing Wang, Hui-Xiong Dai
Summary: The Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is achieved via palladium-catalyzed ligand-promoted C-C bond cleavage, providing good to excellent yields of the alkene product. Further applications in the late-stage olefination of drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By using ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved through sequential ortho-C-H alkylation/ipso-Heck olefination.
