Article
Chemistry, Organic
Joseph M. Anderson, Nicholas D. Measom, John A. . Murphy, Darren L. Poole
Summary: Here, we present a decarboxylative Minisci hetero-arylation study at the bridge positions. Through a simple and photocatalyst-free process, free bridge carboxylic acids are directly coupled with nonprefunctionalized heteroarenes to yield polysubstituted BCP and oBCH derivatives in high yields. Furthermore, the impact of the BCP core on the physicochemical properties of a representative example compared to its all-aromatic ortho- and meta-substituted analogues is evaluated.
Article
Chemistry, Organic
Zezhong Gao, Hang Wang, Chunlin Zhou, Ning Wang, Shangda Li, Gang Li
Summary: In this study, a new C-H functionalization method was reported for the remote site-selective C-H iodination via C(sp(2))-H/C(sp(2))-I metathesis. The mild iodinating reagent, 1-iodo-4-methoxy-2-nitrobenzene, was used to iodinate 2-aryl benzoic acid derivatives, including 2-(naphthalen-1-yl)benzoic acids and [1,1'-binaphthalene]-2-carboxylic acids, giving valuable iodinated products in a site- and chemo-selective manner.
Article
Chemistry, Multidisciplinary
Bo Han, Chunping Ren, Min Jiang, Lipeng Wu
Summary: An unprecedented catalytic reduction method that can convert carboxylic functional groups to methyl groups using titanium as a catalyst has been reported. The system shows broad functional group tolerance and works for various types of oxo-chemicals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chun-Hong Hu, Yueqian Sang, Ya-Wei Yang, Wen-Wen Li, Hui-Lin Wang, ZiYing Zhang, Chen Ye, Li-Zhu Wu, Xiao-Song Xue, Yang Li
Summary: The article presents a solution to the challenge of direct decarboxylation, by utilizing a charge-transfer complex of aryl carboxylate that induces chemoselective decarboxylation to aryl radicals. This method offers potential for mild and versatile arylations in various fields.
Article
Chemistry, Organic
Dan Li, Li Wei, Chaorong Qi, Wenfang Xiong, Hongjian Liu, Huanfeng Jiang
Summary: A palladium-catalyzed direct carbonylation of aryl bromides with carbon dioxide as the carbonyl source has been developed, providing an efficient route to a variety of aryl carboxylic acids in moderate to high yields. The method has many advantages including the use of a simple palladium catalyst system, wide substrate scope, good functional group tolerance, high yields, and easy scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Haipeng Hu, Cuilin Wang, Xin Wu, Yangu Liu, Guizhou Yue, Gehong Su, Juhua Feng
Summary: The catalytic alpha-C-H fluorination of aryl acetic acids was achieved with good functional group tolerance in the presence of a boron catalyst. A series of alpha-fluoro aryl acetic acids were obtained in a single step with high yields (up to 96%). The catalytic reaction was employed for the synthesis of bioactive molecules and the modification of profen drugs.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Viet D. Nguyen, Ramon Trevino, Samuel G. Greco, Hadi D. Arman, Oleg V. Larionov
Summary: Dual catalytic systems involving photocatalytic activation and transition metal-catalyzed steps have enabled innovative approaches to the construction of carbon-carbon and carbon-heteroatom bonds. This study reports a dual catalytic process that enables the direct conversion of carboxylic acids to important synthetic intermediates using a three-component decarboxysulfonylative cross-coupling. Detailed mechanistic and computational studies revealed the roles of different catalysts and ions in channeling the reaction.
Article
Chemistry, Organic
Xue Liu, Long Liu, Tianzeng Huang, Jingjing Zhang, Zhi Tang, Chunya Li, Tieqiao Chen
Summary: The trifluoromethylation of benzoic acids using anhydrides as in situ activating reagents allows for a wide range of carboxylic acids to react efficiently, providing a facile method for preparing aryl trifluoromethyl ketones from readily available starting materials.
Article
Chemistry, Multidisciplinary
Andrey Shatskiy, Anton Axelsson, Elena V. Stepanova, Jian-Quan Liu, Azamat Z. Temerdashev, Bhushan P. Kore, Bjorn Blomkvist, James M. Gardner, Peter Diner, Markus D. Karkas
Summary: A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural alpha-amino acids. The protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.
Article
Chemistry, Organic
James Murray, Maria V. Silva Elipe, Kyle D. Baucom, Derek B. Brown, Kyle Quasdorf, Seb Caille
Summary: The ipso nitration of aryl boronic acid derivatives using fuming nitric acid has been developed, providing an efficient and chemoselective approach to various aromatic nitro compounds. This study reveals that the activation agents and nitro sources reported in the literature likely generate a common active reagent, anhydrous HNO3, with kinetic and mechanistic studies indicating that the (NO2)-N-center dot radical is the active species.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jing Zhang, Ye-Xing Hou, Yan-Liu Tang, Ji-Hang Xu, Zi-Kui Liu, Yang Gao, Xiao-Qiang Hu
Summary: This convenient DMAP-catalysed decarboxylative amination allows for the sustainable synthesis of a wide range of aryl and alkyl amines in useful to good yields without the use of any activating reagent or external oxidant under transition-metal-free conditions. The synthetic potential of this methodology is demonstrated through late-stage modification of bioactive acids and concise synthesis of carbamate and ureas.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Li-Jia Chen, Chia-Jou Kuo, Chien-Fu Liang
Summary: In this study, an efficient method for synthesizing aryl amides from sodium thiosulfate pentahydrate, organic anhydrides, and aryl azides was developed. Sodium thiosulfate acted as the sulfur source, reacting with anhydrides to generate acyl-Bunte salt which then reacted with aryl azides. The method successfully produced a key bioactive compound. The advantages of this one-pot two-step reaction include simplicity, diverse products with high yields, use of non-toxic reagents, and applicability to large-scale operations.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jan Brauer, Elisabeth Quraishi, Lisa Marie Kammer, Till Opatz
Summary: This method utilizes Hantzsch ester as a photoreductant and nickel catalyst to couple various radicals with aryl and alkyl acyl groups. The reaction proceeds under mild conditions without the need for toxic metal reagents or bases, showing wide applicability in pharmaceuticals and complex molecular architectures.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jihye Kim, Jieun Jang, Yoonho Lee, Kwangmin Shin
Summary: In this study, a nickel hydride-catalyzed hydroacylation of aryl alkenes using aroyl fluorides was reported. The reaction proceeds without the need for an exogenous ligand, and the synthetic utility of the method was demonstrated.
Article
Chemistry, Organic
Mo Yu, Kaikai Niu, Ziwen Wang, Yuxiu Liu, Qingmin Wang
Summary: This study presents a protocol for visible-light-induced perfluoroalkylation reactions of aryl acrylic acids, which is important for late-stage modification of biologically active molecules. The reactions proceed in a decarboxylative manner using perfluoroalkyl iodides as radical precursors and inexpensive eosin Y as a photocatalyst. The easy accessibility of perfluoroalkyl iodides and the broad substrate scope, mild conditions, and metal-free catalyst make this protocol applicable for transforming inexpensive raw materials to high-value chemicals.
