Article
Chemistry, Organic
Qi Xia, Xiang Li, Xi Fu, Yaxuan Zhou, Yanqing Peng, Jiayi Wang, Gonghua Song
Summary: A novel three-component reaction catalyzed by CuO in water has been developed, allowing the synthesis of a wide range of products containing 1,3/1,4-diketones. This method offers advantages such as the use of readily available starting materials, wide substrate scopes, excellent yields, gram-scale synthesis, and mild reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Ian A. Tonks
Summary: This study discusses the recent progress in Ti-catalyzed oxidative amination reactions, highlighting the importance of understanding the reactive species and mechanisms involved. The research shows that low-valent Ti intermediates can be stabilized through coordination and that reductive elimination processes occur through pi-type electrocyclic reactions. These findings are crucial for advancing catalytic applications involving titanium.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Tao Dong, Gavin Chit Tsui
Summary: In recent years, the use of inexpensive and earth-abundant copper for fluorination methods has shown significant growth, surpassing methods using palladium and silver in the construction of carbon-fluorine bonds.
Article
Chemistry, Applied
Zhipeng Liu, Xinwei Hu, Can Yang, Haisheng Xie, Huanfeng Jiang, Wei Zeng
Summary: A new method was reported for the synthesis of 2-carbonylethylindole skeletons through Rh(III)-catalyzed Csp(2)-Csp(3) bond cleavage/carbonylethylation of alpha-indolyl alcohols with allylic alcohols. This transformation involved a cascade C-C bond cleavage/C-C bond formation, providing a novel approach for the construction of these complex skeletons.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Chen-Xu Liu, Si-Yong Yin, Fangnuo Zhao, Hui Yang, Zuolijun Feng, Qing Gu, Shu-Li You
Summary: This review summarizes the advancements in rhodium-catalyzed asymmetric C-H functionalization reactions during the last two decades. It has attracted extensive attention due to its unique reactivity and selectivity parallel to the rapidly developed palladium catalysis. In recent years, significant developments have been made in catalyst design, reaction development, mechanistic investigation, and application in the synthesis of complex functional molecules. This review provides an explicit outline of catalysts and ligands, mechanism, the scope of coupling reagents, and applications.
Article
Chemistry, Applied
Geetanjali S. Sontakke, Rahul K. Shukla, Chandra M. R. Volla
Summary: The Rh(I)-catalyzed decarboxylative arylation provides a straightforward platform to access substituted 2,3-allenols and 1,3-butadiene derivatives. The reaction exhibits high regioselectivity and compatibility with various functional groups, allowing the development of a library of diversely functionalized scaffolds with excellent yields. Additionally, late-stage transformation of natural products and downstream transformations highlight the wide applicability and efficacy of the protocol.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jianxiao Li, Dan He, Bowen Wang, Wenfang Xiong, Chaorong Qi, Huanfeng Jiang
Summary: In this paper, a novel and versatile reaction method for the synthesis of alkyl substituted alpha-methylene-gamma-lactones from unactivated alkenes has been reported. This reaction is enabled by Lewis acids and palladium catalysts, and exhibits high yields and excellent Z/E selectivities. The downstream functionalization of (Z)-gamma-lactones allows for the preparation of various valuable complex molecules, and has potential utility in organic synthesis and pharmaceutical chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Shyamal Kanti Bera, Rajat Rajiv Maharana, Kousik Samanta, Prasenjit Mal
Summary: We have demonstrated the activation of the carbonyl group of alpha,beta-unsaturated ketones by weak interactions such as halogen bonding (XB). Carbon tetrabromide (CBr4) has been successfully used as the sole reagent for the selective synthesis of flavanones and aza-flavanones from 2'-hydroxy- and 2'-aminochalcones, without the use of any metals or additives. DFT calculations provide support for the catalytic role of XB between the oxygen of chalcones and CBr4 in these reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Pengcheng Ou, Lei Zhu, Yinghua Yu, Liyao Ma, Xueliang Huang
Summary: In this study, a Xantphos-containing dinuclear palladium complex was used to catalyze the geminal aminoallylation of diazocarbonyl compounds, providing a selective synthesis of various quaternary alpha-amino esters. The reaction did not proceed through direct N-H insertion, allylic alkylation of amino nucleophiles, or diene formation. Mechanistic investigations indicated that a relayed pathway via allylation or a [2,3]-sigmatropic rearrangement was unlikely.
Article
Chemistry, Organic
Can Yang, Zhipeng Liu, Xinwei Hu, Haisheng Xie, Huanfeng Jiang, Wei Zeng
Summary: The study reported a Rh(iii)-catalyzed direct Csp(2)-Csp(3) bond alkoxylation of alpha-(2-indolyl)alcohols with alcohols, featuring a rapid switch between C-C sigma bond and C-O single bond, providing a novel approach for assembling 2-alkoxylindole skeletons. A catalytic cycle involving a beta-aryl elimination process was proposed.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Chao Hong, Shuling Yu, Zhanxiang Liu, Yuhong Zhang
Summary: A coupling reaction of acrylic acids/benzoic acids with alpha-diazocarbonyl compounds has been achieved using a combined catalytic system of rhodium catalyst and Zn(OAc)(2) additive. The presence of Zn(OAc)(2) facilitates the C(sp(2))-H activation and disrupts the formation of carboxylic ester via nucleophilic O-H insertion to metal carbenoid. This method offers mild reaction conditions and broad substrate scope, providing a convenient and direct approach for the synthesis of alpha-pyrones and isocoumarins without the need for carboxylic acid transformation to amides.
Article
Chemistry, Organic
Eunjae Chung, Suho Kim, Amitava Rakshit, Pargat Singh, Jaewook Park, Taejoo Jeong, In Su Kim
Summary: In this study, the rhodium(III)-catalyzed C8-spiroannulation of 1-aminonaphthalenes with maleimides is investigated. The resulting C8-alkenylated 1-aminonaphthalenes can further react with nucleophilic 1-amino groups through intramolecular aza-Michael reaction, leading to the formation of spirofused tetracyclic frameworks. This method demonstrates a broad substrate scope and compatibility with various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Linxing Zhang, Kun An, Yi Wang, Yun-Dong Wu, Xinhao Zhang, Zhi-Xiang Yu, Wei He
Summary: This study elucidates the reaction pathway and a more efficient catalyst for C-H silylation through a combination of computational and experimental methods, providing a foundation for further research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Yang Zhao, Xinyue Niu, Hong Yang, Jing Yang, Zhizeng Wang, Qilin Wang
Summary: In this study, a substrate-directed diverse synthetic strategy was reported for the synthesis of two kinds of structurally intriguing fused indole polycycles through Rh(ii)-catalyzed cascade reactions. The subtle structural changes in enaminones result in different reactivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Anurag Singh, Rahul K. Shukla, Chandra M. R. Volla
Summary: In this study, a novel Ru(II)-catalyzed non-oxidative [5+1] annulation reaction was developed to access biologically relevant chromene skeletons. The heteroatom on allene was found to control the regioselectivity of migratory insertion, and the reaction proceeded through a Ru-sigma-allyl pathway, which is unprecedented in C-H activation reactions with allenes. This sustainable protocol was carried out at room temperature without the use of any toxic metal oxidants. The synthetic utility of the method was demonstrated by late stage functionalization and modular synthesis of various natural product conjugates.