Article
Chemistry, Organic
Dian Yu, Si-Yuan Peng, Han Wang, Qiu-Cui Zheng, Ya-Hui Ma, Dong-Yi Xiao, Qian-Li Li, Wen-Shu Wang, Xiao-Jie Cui, Fei-Xian Luo
Summary: In this work, a one-pot strategy was developed for the precise modification of amides derived from natural amino acids via Pd/Cu-catalyzed cascade γ-C(sp(3))-H arylation/C-N coupling. This strategy successfully synthesized valuable chiral 2-functionalized tetrahydroquinoline motifs with good chirality maintenance. It offers an alternative route for the synthesis of chiral tetrahydroquinolines with good regioselectivity and broad functional group compatibility for drug discovery. The methodology has also been demonstrated for the late-stage functionalization of natural products, drugs, and biomolecules.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jilei Cao, Xiaona Yang, Lishuang Ma, Kanghui Lu, Rong Zhou
Summary: A synergistic combination of photoredox and polarity reversal catalysis enabled a novel approach for the generation of silyl cation via visible-light photoredox catalysis, facilitating the dehydrogenative cross-coupling of Si-H and O-H in good yields and broad substrate scope. The reaction proceeded smoothly without the need for any metals, external oxidants, or proton reductants, unlike traditional photocatalytic hydrogen evolution cross-coupling reactions.
Article
Chemistry, Multidisciplinary
Xiaoyu Cheng, Baojun Li, Mengsi Zhang, Haotian Lu, Wenbo Wang, Yun Ding, Aiguo Hu
Summary: A novel free radical-initiated reaction between cyclic ethers and maleimide iodides through C-H activation has been developed, providing a simple approach to derive cyclic ethers without using transition metallic catalysts. These cyclic ethers can be further applied in various cross coupling reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yueyao Feng, Jie Wang, Jie Yang, Fengyuan Chen, Zemin Zhang, Chongrong Ke, Jin Lin, Hua Lin
Summary: Selective remote C-H activation of amines using unmodified NH2 as a directing group is synthetically valuable. The selective iodination of 3-arylpropan-1-amines provides valuable intermediates for modifying bioactive molecules and synthesizing quinolones. This study reports the first palladium-catalyzed selective epsilon-C(sp(2))-H iodination of free 3-arylpropan-1-amines via a seven-membered palladacycle.
Article
Chemistry, Multidisciplinary
Jiachen He, Silas P. Cook
Summary: Here, a metal-free, photo-induced borylation method for unactivated C(sp(3))-H bonds adjacent to an O-oxalate hydroxamic ester functionality is described. The protocol utilizes substrate and bis(catecholato)diboron under light irradiation to achieve the desired transformation. This approach enables the selective late-stage C(sp(3))-H borylation of natural product derivatives and drug-like compounds, yielding a range of linear and cyclic tertiary and secondary borylation products with good yields.
Article
Chemistry, Multidisciplinary
Xiaojie Shan, Pan Gao, Shuwei Zhang, Xiaodong Jia, Yu Yuan
Summary: This article reports a method for synthesizing β-nitrostyrene and ether compounds through radical addition reaction under mild conditions without any other additives. In most cases, the synthesis reaction has good results, and the reaction system has the advantages of high reactivity and strong stability. It is particularly useful in the pharmaceutical industry.
Article
Chemistry, Organic
Xiao-Wen Wang, Rui-Xue Li, Yang Deng, Ming-Qiu-Hao Fu, Ya-Nan Zhao, Zhi Guan, Yan-Hong He
Summary: This article proposes a new method for the direct hydroxylarylation of unactivated benzylic carbons (sp3/sp2/sp) without the need for pre-functionalized benzylic alcohols, aromatic aldehydes, or ketones. It features direct functionalization of unactivated benzylic C(sp3)-H bonds and benzylic sp2/sp-carbons, mild conditions (open air, room temperature), an environmentally friendly procedure (without any external catalyst/mediator/additive), and direct access to sterically hindered alcohols from inexpensive and readily available alkyl/alkenyl/alkynylbenzenes. Mechanistic studies strongly support the proposed radical-radical cross-coupling between transient ketyl radicals and persistent radical anions. Gram-scale synthesis and diversification of drug derivatives demonstrate the practical potential of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Xiaochen Wang, Rongxin Yang, Binbing Zhu, Yuxiu Liu, Hongjian Song, Jianyang Dong, Qingmin Wang
Summary: Here, the authors describe a multicatalytic method for the synthesis of beta, gamma-unsaturated ketones via allylic acylation of alkenes. The method combines N-heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for cross-coupling reactions. The method shows excellent site selectivity and could be used for the synthesis of diverse beta, gamma-unsaturated ketones using carboxylic acids and olefins as substrates.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Organic
Danhua Ge, Xin Wang, Xue-Qiang Chu
Summary: This review provides an overview of recent advancements in alkynylation using acetylenic sulfones, highlighting their role in the synthesis of alkynes, fluoroalkylated compounds, sulfonylated compounds, and in situ SO2 capture. The article discusses direct alkynylation with various C-centered radicals and multi-step reaction modes involving acetylenic sulfones, while emphasizing the generality of substrate scope and proposed mechanisms.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Zining Zhang, Qi Zhu, Daniel Pyle, Xukai Zhou, Guangbin Dong
Summary: This study reports a deacylative halogenation approach to convert various methyl ketones to alkyl halides by forming an aromatic byproduct. The method is applicable to a wide range of methyl ketones and can be used for one-pot conversions and annulations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Zhi-Wei Zhao, Yu-Song Ran, Yu-Jian Hou, Xin Chen, Xue-Ling Ding, Cui Zhang, Ya-Min Li
Summary: Free radical carbochloromethylation reactions of ortho-cyanoarylacrylamides and N-(arylsulfonyl)acrylamides have been developed using simple alkyl chlorides as the chloromethyl source. These transformations exhibit wide functional group compatibility and provide efficient methods for constructing polychloromethyl-substituted quinoline-2,4-diones and alpha-aryl-beta-polychloromethylated amides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jing Gui, Manman Sun, Haijian Wu, Jinshan Li, Jianguo Yang, Zhiming Wang
Summary: A visible light promoted direct benzylic C-H difluoroalkylation reaction has been developed using a transition metal-free organic photocatalyst, Na-2-eosin Y, via a HAT-ORPC pathway. This method provides an efficient and atom-economic approach for the difluoroalkylation of C(sp(3))-based substrates. It shows great advantages in environmental friendliness with mild reaction conditions and the use of air as a green oxidant. Various substituted xanthenes, acridines, and thioxanthene are found to be efficient substrates for constructing pharmaceutically important alpha-benzyl-alpha,alpha-difluoroketones with yields up to 96%.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Zhenbang Chang, Saisai Zhang, Yinpeng Wang, Heng-Ying Xiong, Guangwu Zhang
Summary: This study demonstrates the coupling between heterocyclic N-oxides and CF3-ynones via formal C-H and C-C bond cleavage under catalyst-free and mild conditions. The reaction shows a broad substrate scope and potential application.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Guo-Qiang Xu, Teng-Fei Xiao, Guo-Xuan Feng, Chen Liu, Baoxin Zhang, Peng-Fei Xu
Summary: The metal-free C(sp(3))-H aroylation of amines via visible-light photoredox catalysis provides a direct route for constructing a useful a-amino aryl ketone skeleton. Selected products show good biological activity for protecting PC12 cells, indicating the potential of this skeleton as a new neuroprotective agent. Mechanism experiments suggest that this transformation follows a photoredox catalytic radical-radical cross-coupling pathway.
Article
Chemistry, Organic
Gi Hoon Ko, Kyusik Um, Hee Chan Noh, Jin Young Kim, Haneal Jeong, Chanyoung Maeng, Sang Hoon Han, Gi Uk Han, Phil Ho Lee
Summary: Here, we demonstrate a regioselective acylmethylation of the cage B(4)-H bond in o-carborane acids using iridium(III) catalyst and sulfoxonium Aides under mild conditions. This reaction affords various B(4)-acylmethylated o-carboranes. Furthermore, by selectively conducting sequential B(4)- and B(6)-acylmethylation reactions, B(3,5)-diacylmethylated o-carboranes can be obtained in a one-pot manner.
