Article
Chemistry, Multidisciplinary
Yang Gao, Benxiang Zhang, Laura Levy, Hai-Jun Zhang, Chi He, Phil S. Baran
Summary: This article reports the first enantioselective decarboxylative Negishitype alkylations of alpha-oxy carboxylic acids via the intermediacy of redox-active esters (RAEs). The transformation enables the radical-based retrosynthesis of seemingly trivial enantiopure dialkyl carbinols. The article discusses the history of such couplings, the retrosynthetic ramifications, general conditions development, and showcases various applications that demonstrate its simplification effect on synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Roberto do Carmo Pinheiro, Luiz Eduardo Welter, Bernardo A. Iglesias, Davi F. Back, Luiza Souza Marques, Cristina Wayne Nogueira, Gilson Zeni
Summary: Heterocycles fused to seven-membered rings were synthesized in a highly selective manner using potassium tert-butoxide-catalyzed one-pot cyclization. Systematic study revealed that a catalytic amount of potassium tert-butoxide, dimethyl sulfoxide, and the tert-BuOK/tert-BuOH equilibrium played crucial roles in the formation of products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xingwei Cai, Yang Shen, Wei Li, Wentao Zhan, Fanjun Zhang, Chen Xu, Heng Song
Summary: In this study, an efficient tungsten-catalyzed homogeneous system was developed for the selective synthesis of various azoaromatics, azoxyaromatics, and 2-substituted indolone N-oxides from anilines. This was achieved by regulating the reaction solvent with peroxide as a terminal oxidant under additive-free conditions. These findings not only provide an experimental framework for exploring tungsten catalysis in organic synthesis but also offer an efficient and convenient tactic for the selective oxidation of anilines.
Article
Chemistry, Organic
Kartic Manna, Tanusree Ganguly, Sujoy Baitalik, Ranjan Jana
Summary: This method enables a metal-free, visible-light- and triphenylphosphine-mediated intermolecular reductive amination between nitroarenes and boronic acids at ambient temperature without any photocatalyst. Mechanistically, a slow reduction of nitroarenes to a nitroso and, finally, a nitrene intermediate occurs that leads to the amination product with concomitant 1,2-aryl/alkyl migration from a boronate complex. A wide range of nitroarenes underwent C-N coupling with aryl/alkylboronic acids providing high yields.
Article
Chemistry, Organic
Qianqian Liu, Zheng Zhou, Zhibin Huang, Yingsheng Zhao
Summary: A palladium-catalyzed oxidative amination of inactive olefins with an aromatic amine using a copper acetate oxidant was developed, yielding corresponding secondary and tertiary enamines in moderate to good yields. This new procedure outlines an efficient approach for the construction of enamine skeletons.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Zuguang Yang, Pinyi Li, Zhengkai Chen, Xiao-Feng Wu
Summary: A rhodium(III)-catalyzed C-H activation/[4+1] annulation reaction has been developed for the synthesis of diverse trifluoroacetimidoyl-substituted 11H-isoindolo[2,1-a]indoles. The reaction cascade involves C-H imidoylmethylation, tautomerization, and AgOAc-mediated C-N bond formation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Ming Li, Yuke Li, Wan-Yuan Jia, Guo-Qing Sun, Fan Gao, Guo-Xiao Zhao, Yi-Feng Qiu, Xi-Cun Wang, Yong-Min Liang, Zheng-Jun Quan
Summary: The free radical cyclization reaction is a promising strategy for the formation of ring frameworks. In this study, we report a copper-catalyzed tandem radical cyclization strategy for preparing substituted lactam derivatives. This reaction utilizes a radical coupling approach, allowing a wide range of alkenes and being compatible with primary, secondary, and tertiary radicals. Density functional theory calculations were also performed to gain insights into the reaction mechanism.
Article
Chemistry, Organic
Yinsong Wu, Xinwei He, Mengqing Xie, Ruxue Li, Yi Ning, Jiahui Duan, Enshen Zhang, Yongjia Shang
Summary: The Rh(III)-catalyzed cascade nucleophilic addition/intramolecular annulation of 2-diazo-1,3-diketones with 1,3-dicarbonyl compounds has been successfully achieved to yield 6,7-dihydrobenzofuran-4(5H)-ones in up to 91% yields. The reaction tolerates a wide range of substrates and functional groups under optimized conditions and is scalable and adaptable to late-stage functionalization.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Francisco Villalba, Ana C. Albeniz
Summary: Hydrazones play a crucial role as ligands in palladium-catalyzed cross coupling reactions, but their interaction with palladium and reaction mechanism remain understudied.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Yoshihiko Yamamoto, Harufumi Suzuki, Eisuke Kuroyanagi, Keiji Yamada, Takeshi Yasui
Summary: In this study, the atom transfer radical addition (ATRA) of bromodifluoroacetamides to arylalkynes and terminal alkenes was successfully conducted using von Wangelin's Co catalyst system. The corresponding functionalized difluoroacetamides were obtained in moderate to high yields. Additionally, the Co catalyst was applied to tandem addition/cyclization reactions of 1,6-diene and -enyne substrates, as well as intramolecular ATRA of N-allyl and N-propargyl bromodifluoroacetamides, significantly expanding the scope of radical difluoroalkylation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shohei Furuya, Kazuya Kanemoto, Shin-ichi Fukuzawa
Summary: This study describes an unprecedented Ag-catalyzed exo'-selective [3+2] cycloaddition reaction between imino esters and 4-benzylidene-2,3-dioxopyrrolidines. The reaction, efficiently catalyzed by Ag/(R, S-p)-ThioClickFerrophos (TCF), allows for the construction of spirobipyrrolidine scaffolds with excellent enantio- and diastereoselectivities. It is the first example of a silver-catalyzed exo'-selective asymmetric [3+2] cycloaddition and the first exo'-selective spirobipyrrolidine construction process using imino esters. The broad substrate scope of this reaction enables the synthesis of diverse spirobipyrrolidine derivatives, which are of interest for drug discovery. Mechanistic studies suggest that the unusual exo'-selectivity of this reaction is due to a stepwise Michael addition/Mannich sequence with bond rotation, rather than epimerization following the common exo- or endo-selective cycloaddition.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Zhi-Peng Han, Meng-Meng Xu, Rui-Ying Zhang, Xiao-Ping Xu, Shun-Jun Ji
Summary: This rhodium-catalyzed synthesis method for indoloquinazolinone from a readily available hypervalent iodonium reagent and N-carboxamide indole is characterized by broad functional group tolerance, mild conditions, and excellent yields. The target products can be obtained simply by filtration, without tedious column chromatography, and the noble metal catalyst system can be effectively recycled at least ten times, making it potentially suitable for industrial production.
Article
Chemistry, Organic
Biwei Yang, Linhong Zuo, Xiaowei Chang, Teng Liu, Manying Cui, Yang Liu, Haiyu Sun, Weipeng Chen, Wusheng Guo
Summary: A decarboxylative protocol using cyclic carbonates as substrates has been developed to synthesize carbocycles, with controllable kinetics towards strained seven- or more thermodynamically favored five-membered rings. The release of this chemistry will benefit the synthesis of complex and valuable cyclic structures.
Article
Chemistry, Organic
Ruben M. Carballo, Jose M. Padron, Israel Fernandez, Daniel A. Cruz, Luana Grmus, Victor S. Martin, Juan I. Padron
Summary: A direct, catalytic, and complementary method for the synthesis of 2-substituted homoallyl sulfonyl amides from sulfonyl amides, aldehydes, and allyltrimethylsilane using iron(III) chloride as a sustainable catalyst is described. The scope of the reaction and its reactivity in aza-Prins cyclization are evaluated with the support of density functional theory (DFT) studies. The antiproliferative activity of this family of sulfonyl amides is also assessed.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Domenic P. Pace, Raphael Robidas, Uyen P. N. Tran, Claude Y. Legault, Thanh Vinh Nguyen
Summary: A practical and mild catalytic method for the synthesis of substituted pyrans and furans using molecular iodine has been reported, offering a facile alternative under solvent-free conditions at ambient temperature and atmosphere. Mechanistic insights into this seemingly simple reaction were revealed through a combination of experimental studies and density functional theory calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.