Article
Chemistry, Applied
Chuanfu Hou, Shouneng Sun, Ziqi Liu, Hui Zhang, Yue Liu, Qi An, Jian Zhao, Junjie Ma, Zhizhong Sun, Wenyi Chu
Summary: This study reports the development of a visible-light-induced catalytic system for the decarboxylative acylation of pyridine N-oxides with alpha-oxocarboxylic acids, using fluorescein dimethylammonium as a new type of photocatalyst. A series of 2-arylacylpyridine N-oxides were selectively synthesized by controlling the polarity of the reaction solvent. The disclosed catalytic system provides a green synthetic strategy for decarboxylative acylation without the use of additional oxidants or metal catalysts.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Shanshan Liu, Pingjun Zhang, Yuanyuan Zhang, Xianying Zhou, Jiahui Liang, Jiang Nan, Yangmin Ma
Summary: A novel method was developed for the synthesis of quinoxalines catalyzed by an acid-functionalized ionic liquid, which showed high tolerance towards various functional groups and could be easily scaled up in water. The developed method featured a recyclable catalytic system, environmentally friendly reaction conditions, simple operation, and a practical workup procedure, suggesting its potential for industrial application in streamlining quinoxaline synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Liwei Zhou, Mingjie Sun, Fengru Zhou, Guobo Deng, Yuan Yang, Yun Liang
Summary: A novel palladium-catalyzed divergent decarboxylative cyclization of 2-iodobiphenyls and alpha-oxocarboxylic acids utilizing the atmosphere as a controlled switch has been reported. Under the protection of a nitrogen atmosphere, tribenzotropones are synthesized by a [4 + 3] decarboxylative cyclization. Employing a palladium/O-2 system enables a [4 + 2] decarboxylative cyclization to assemble triphenylenes. Preliminary mechanistic studies suggest that the formation of triphenylenes involves a double decarboxylation.
Article
Chemistry, Organic
Feng Zhao, Na Meng, Ting Sun, Jiangwei Wen, Xiaohui Zhao, Wei Wei
Summary: A mild and environmentally benign electrochemical strategy has been developed to synthesize alpha-ketoamides via decarboxylative coupling reaction of alpha-keto acids with isocyanides and water. This efficient reaction can be conducted under constant current electrolysis without the need for transition metal catalysts or external oxidants. Mechanistic studies indicate that water not only serves as a starting material for constructing alpha-ketoamides but also plays a crucial role in promoting the electrochemical redox of alpha-keto acids.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Yang Gao, Phil S. Baran
Summary: A new approach to the enantiocontrolled synthesis of alpha-amino ketone derivatives is presented using a decarboxylative acylation strategy. This method yields the desired alpha-amido ketones with good yield and high enantioselectivity when an acyl chloride and an alpha-amido-containing redox-active ester are exposed to a nickel catalyst, chiral ligand, and metal reductant. The reaction has wide substrate scope, scalability, and simplifies the synthesis of known structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yuping Zhu, Tianqi Liu, Bingxin Liu, Houguang Shi, Qitao Tan, Bin Xu
Summary: In this study, alpha-Keto acids were used as novel precursors of nitrile oxides upon treatment with copper nitrate, which reacted with maleimides via [3 + 2] dipolar cycloaddition to form pharmacologically interesting fused isoxazolines. Compared with previous methods, this approach provides a unique and complementary strategy for the convenient synthesis of alkyl substituted nitrile oxides. Mechanistic studies revealed a novel carbon-carbon bond cleavage in alpha-keto acids leading to key gem-dinitroalkane intermediates for the transformation to nitrile oxides in 1,3-dipolar cycloadditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Zhiyong Wu, Shuai Hao, Jingyan Hu, Hongtao Shen, Miao Lai, Pengfei Liu, Gaolei Xi, Pengfei Wang, Shengchen Zhao, Xiaoping Zhang, Mingqin Zhao
Summary: This novel and facile synthesis of aryl benzyl sulfones was achieved for the first time through a copper-catalyzed decarboxylative reductive sulfonylation reaction between alpha-oxocarboxylic acids and aryl sulfonyl hydrazines. The protocol proceeds smoothly under simple conditions, offering advantages of simple operation, high yields, and good functional group compatibility. This approach introduces a conceptually novel methodology for aryl benzyl sulfone synthesis under a decarboxylative reductive progress.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shruti Rajput, Ramandeep Kaur, Nidhi Jain
Summary: The directing group assisted decarboxylative ortho-benzoylation of N-aryl-7-azaindoles with alpha-keto acids has been achieved by synergistic visible light promoted photoredox and palladium catalysis. The approach offers a rapid method for the synthesis of aryl ketones from simple alpha-keto acid precursors via generation of a benzoyl radical intermediate. The resulting compounds exhibit excellent site-selectivity and good functional group compatibility, suggesting potential anti-cancer and anti-viral activities.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Shengqiang Wang, Xiaobo Xu, Dapeng Zou, Qijie Xu
Summary: This method utilizes alpha-keto acids as acylation reagent in aqueous media for Ag-Catalyzed decarboxylative acylation of pyridazines, providing a new avenue for synthesizing a diverse array of acylated pyridazines with different substitution patterns. The reaction proceeds smoothly under mild conditions in water, exhibiting good functional group tolerance.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Lipeng Long, Jieyan Wang, Liuqing Gu, Shiguang Yang, Liang Qiao, Guotian Luo, Zhengwang Chen
Summary: A novel catalyst-free radical oxidative C-H annulation reaction was developed for the synthesis of benzoxazin-2-ones, using arylamines and alpha-keto acids. The process, promoted by hypervalent iodine(III), eliminates the need for metal catalysts or additives and exhibits high functional group tolerance. The utility of this method was demonstrated through the synthesis of the natural product cephalandole A.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Biquan Xiong, Lulu Si, Longzhi Zhu, Yu Liu, Weifeng Xu, Ke-Wen Tang, Shuang-Feng Yin, Peng-Cheng Qian, Wai-Yeung Wong
Summary: A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement is reported. The reaction can be carried out effectively without the use of a ligand and a base. Various aryl acrylic acids and P(III)-nucleophiles are compatible in this transformation, providing β-keto-organophosphorus compounds with good to excellent yields. The possible mechanism and kinetic studies show that this transformation may proceed through second-order chemical kinetics and involves a radical process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Liwei Zhou, Shujia Qiao, Fengru Zhou, Xinyu Xuchen, Guobo Deng, Yuan Yang, Yun Liang
Summary: A novel palladium-catalyzed decarboxylative cascade cyclization for the assembly of diverse fused heteropolycycles has been reported. The approach enables the simultaneous construction of six- and seven-membered rings via intramolecular carbopalladation, C-H activation, and decarboxylation.
Article
Chemistry, Organic
Feng Zhao, Sa Guo, Yan Zhang, Ting Sun, Bing Yang, Yong Ye, Kai Sun
Summary: A practical Ag-catalyzed decarboxylative difluoroalkylation-carbocyclization reaction was reported, yielding various gem-fluorinated quinolinones in moderate to good yields. Mechanistic studies suggested a pathway involving formal decarboxylation and subsequent radical difluoroalkylation-carbocyclization.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Organic
Ajijur Rahaman, Shivani Singh Chauhan, Sukalyan Bhadra
Summary: Chemists have been studying the important transformations of carboxylic acids, which are safe and easily accessible with diverse structures. Carboxylic acids have long been recognized as adaptable starting materials in organic synthesis. The field of catalytic decarboxylative transformations has expanded significantly in the past 20 years, utilizing various classes of carboxylic acids as substrates. This review provides an overview of decarboxylative transformations of α-keto acids, α,β-unsaturated acids, and alkynoic acids developed since 2017, focusing on reactions with or without transition metal catalysts and/or photoredox catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jingjing Wang, Xue Liu, Ziyan Wu, Feng Li, Tingting Qin, Siyuan Zhang, Weiguang Kong, Lantao Liu
Summary: The silver-catalyzed decarboxylative C-H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been achieved under mild reaction conditions, producing moderate to good yields (32%-91%). The study also demonstrated the potential of the technology in gram-scale reactions and late-stage modification of drugs.
CHINESE CHEMICAL LETTERS
(2021)
