Article
Chemistry, Organic
Vera A. Vil, Evgenii S. Gorlov, Bing Yu, Alexander O. Terent'ev
Summary: The oxidative C-O coupling of cyclic diacyl peroxides with acetals enables the selective functionalization of the non-activated acetal alpha-position. The reaction produces alpha-acyloxy acetals with a free carboxylic acid group in yields ranging from 42-85%.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Shuaizhong Zhang, Jinquan Zhang, Hongbin Zou
Summary: Pd(II)-catalyzed oxidation of terminal olefins to methyl ketones using tert-butyl hydroperoxide and 2-(1H-indazol-1-yl)quinoline as the oxidant and ligand, respectively, was reported. Various olefins were well tolerated in this reaction system, providing methyl ketones, and acetoxylation products were obtained in the presence of Ac2O. Isotope labeling studies and active-intermediate-capture experiments revealed the underlying selective reaction mechanism, with the generation of acetoxylation products involving palladium enolate intermediate and methyl ketone products generated through alkylperoxide intermediates followed by 1,2-hydride migration.
Article
Chemistry, Applied
Nagarajan Ramkumar, Arturs Sperga, Sergey Belyakov, Anatoly Mishnev, Dzintars Zacs, Janis Veliks
Summary: Fluoroalkyl ethers have been extensively researched in the fields of pharmaceutical, agrochemical, nuclear imaging, and material sciences, leading to the development of new synthetic methods. Radical fluoroalkoxylation has emerged as a promising approach for synthesizing fluoroalkyl ethers. This study introduced a solid, easily accessible redox-active N-O reagent, 1-(fluoromethoxy)-3-methyl-benzotriazolium triflate (FMBT), which acts as a radical source of (mono)fluoromethoxy group under photocatalytic conditions. The synthetic potential of FMBT was demonstrated in the functionalization of olefins to obtain amino and ketomonofluoromethyl ethers, contributing to the study of chemical biology and drug discovery.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Canlin Zou, Hongting Wu, Jiangtao He, Yunfei Hu, Weijie Deng, Xinling Li, Jinhui Hu, Yibiao Li, Yubing Huang
Summary: An efficient anodic C(sp(3))-H acyloxylation protocol has been developed, which enables the direct oxidation of indolin-3-ones to obtain various C2-acyloxy indolin-3-ones without the need for metal catalysts and external oxidants. The practicality of this protocol has been demonstrated through the effective application of several medical drugs and gram-scale experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Muhammet Uyanik, Hiroki Tanaka, Kazuaki Ishihara
Summary: A chemoselective tandem oxidative cyclization/aromatization of indole derivatives tethered to aniline sulfonamides was reported using catalytic tetrabutylammonium iodide and TBHP under nearly neutral conditions at room temperature. The corresponding indolo[2,3-b]quinolines could be easily isolated in pure form via simple filtration, leading to the natural product quinindoline. Control experiments showed the generation of both ionic and radical active species in situ under mild conditions for chemoselective oxidative transformations.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Marina Briand, Linh D. Thai, Flavien Bourdreux, Nicolas Vanthuyne, Xavier Moreau, Emmanuel Magnier, Elsa Anselmi, Guillaume Dagousset
Summary: Site-selective trifluoromethylation of silyl dienol ethers derived from alpha,ss-unsaturated aldehydes, ketones, and amides was achieved for the first time in the remote gamma position. An unprecedented enantioselective C(sp(3))-H perfluoroalkylation process is disclosed.
Article
Chemistry, Multidisciplinary
Yu-Bin Wang, Fei Chen, Min Li, Qingqing Bu, Zhihong Du, Jichang Liu, Bin Dai, Ning Liu
Summary: Visible light-promoted strategies were developed for the synthesis of gem-dihaloenones using alkynes and polyhalomethanes as the starting materials. The methods produce a broad range of gem-dibromoenones and gem-dichloroenones without using photocatalysts or additives, such as bases and oxidants. This is the first example of a photocatalyst-free strategy for the photo-promoted synthesis of gem-dihaloenones. These protocols were compatible with various terminal and internal alkynes and were effective in gram-scale experiments.
Article
Chemistry, Organic
Michiel T. Uiterweerd, Adriaan J. Minnaard
Summary: The first total synthesis of the complex rearranged angucyclinones Elmonin and Pratenone A is reported in this study. The key naphthalene fragment present in both targets was efficiently prepared using peri-directed C-H functionalization. Coupling with two anisole-derived fragments led to the synthesis of the natural products, with Elmonin being prepared using a biomimetic spiro-ketalization.
Article
Chemistry, Multidisciplinary
Anna Bay, Emelia J. Farnam, Karl A. Scheidt
Summary: This study presents a novel tandem carbene and photoredox-catalyzed process for the synthesis of substituted cycloalkanones, offering a new approach for constructing important cyclic scaffolds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Fan Wu, Yu Guo, Zihao Ren, Zixuan Chen, Xiaoqin Liu, Chang Wang, Liangce Rong
Summary: In this study, the efficient intermolecular alkoxylation reactions of various enol acetates and different alcohols were developed for the first time in the electrochemical process. Enol acetates derived from either aromatic, alkyl, or alicyclic ketones, and abundant free alcohols directly used in this synthetic strategy, make this transformation very valuable in synthesis and application in the future.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ying-Ying Peng, Bi-Yin Zhuo, Zhi-Qiang Wang, Bang Liu, Fu-Xing Zhang, Jiang-Xi Yu, Cheng-Yong Wang, Zhi-Feng Xu, Jin-Heng Li
Summary: A room temperature Mg((OBu)-Bu-t)(2)-catalyzed C(sp(3))-H oxidation of alpha-azido arylethanones to produce primary alpha-ketoamides is presented. By utilizing TBHP as the oxidant and carbonyl oxygen source, this method allows the oxidation of dual methylene C-H bonds alpha to the carbonyl group for the synthesis of various primary alpha-ketoamides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Mouxin Huang, Long Zhang, Tianrun Pan, Sanzhong Luo
Summary: This study presents a distinctive photochemical E/Z isomerization strategy for the deracemization of α-branched aldehydes, which involves the use of simple aminocatalysts and readily available photosensitizers. The method enables the direct transformation of racemic α-branched aldehydes into enantiopure α-tertiary carbonyls with high selectivity.
Article
Chemistry, Applied
Shuang Wu, Yiyun Chen
Summary: In this study, we demonstrate the alpha-C-H acyloxylation of sulfides and disulfides using hypervalent iodine(III) reagents and photoredox catalysis. Methoxylbenziodoxole derivatives act as hydrogen atom transfer agents, mild oxidants, and acyloxylation sources in the reaction. External nucleophiles can also be introduced to the alpha-C-H of sulfides. This reaction is applicable to various aryl and alkyl sulfides, including methionine peptide derivatives. Disulfides can be used for the first time with excellent chemoselectivity and functional group compatibility.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Fabrice Gallou, Harald Groeger, Bruce H. Lipshutz
Summary: Biocatalytic processes and chemoenzymatic catalysis are attractive to fine chemical companies due to their selective and environmentally friendly nature. Integration of chemocatalysis and biocatalysis in aqueous media allows for more efficient processes. However, industrial usage is currently variable.
Article
Chemistry, Multidisciplinary
Huamin Wang, Meng He, Yongli Li, Heng Zhang, Dali Yang, Masanari Nagasaka, Zongchao Lv, Zhipeng Guan, Yangmin Cao, Fengping Gong, Zhilin Zhou, Jingyun Zhu, Supravat Samanta, Abhishek Dutta Chowdhury, Aiwen Lei
Summary: A highly selective, environmentally friendly, and scalable electrochemical protocol for constructing alpha-acyloxy sulfides has been developed, utilizing the synergistic effect of self-assembly-induced C(sp(3))-H/O-H cross-coupling. This protocol demonstrates broad substrate scope, high regioselectivity, gram-scale synthesis, construction of complex molecules, and applicability to various nucleophiles. The pivotal role of substrate self-assembly has been confirmed through soft X-ray absorption technique and control experiments, contributing to the excellent compatibility and precise regioselectivity control in the electrochemical protocol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Bo Yang, Zhong-Xia Wang
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Wei-Can Dai, Bo Yang, Shi-He Xu, Zhong-Xia Wang
Summary: The reaction of aryl 2-pyridyl ethers with arylzinc reagents catalyzed by NiCl2(PCy3)(2) can achieve aryl-aryl cross-coupling with a wide range of substrates and good functional group compatibility. It was found that beta-H-free alkylzinc reagents are more suitable as nucleophiles in this transformation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Guang-Li Xu, Zhong-Xia Wang
Summary: Regioselective silylation of 2,3-allenols with disilanes was achieved under the catalysis of Pd(2)dba(3)/P(o-MeOC6H4)(3). The presence of Cs2CO3 led to the formation of 2-silyl-1,3-dienes. The reaction showed different selectivities and major isomers depending on the substrate used.
Article
Chemistry, Organic
Hong Miao, Zhong-Xia Wang
Summary: A ruthenium-catalyzed oxidative cross-coupling reaction of alkenes with triisopropylsilylacetylene was achieved, directed by 2-pyridyl or 2-pyrimidyl groups. This protocol showed good compatibility with various functional groups and exhibited Z-selectivity for the enyne products.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Guang-Li Xu, Zhong-Xia Wang
Summary: Conjugated polyenes with allylic amino and hydroxy groups were successfully synthesized through the palladium-catalyzed reaction of 2,3-allenols with amines. Using MeOH as the solvent led to (Z)-configured [3]dendralene derivatives, while using iPrOH as the solvent resulted in (1Z,3E)-1,3-diene derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: This article describes the rhodium-catalyzed P(III)-directed aromatic C-H acylation reaction with amides. The reaction features a simple catalyst system, mild reaction conditions, monoacylation selectivity, a wide scope of substrates, and good compatibility of functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Guang-Li Xu, Yu-Tong Duan, Zhong-Xia Wang
Summary: In this study, the reaction of 2,3-allenols with PhMe2SiZnCl or Ph2MeSiZnCl under the catalysis of IPrCuCl or SIPrCuCl was carried out, resulting in the formation of 2-silyl-1,3-butadienes. Both secondary and tertiary 2,3-allenols could be used as coupling partners. The reaction of secondary 2,3-allenols exclusively gave (E)-2-silyl-1,3-butadienes as the products.
Article
Chemistry, Applied
Xue-Yi He, Zhong-Xia Wang
Summary: The ruthenium(II)-catalyzed reaction between aniline derivatives and allylamines was used to synthesize 2-methylindoles via C-H/C-N bond activation. The most effective directing group is the 4,5-dimethyl pyrimidin-2-yl group attached on the nitrogen atom of anilines, while N-allyl-4-fluoro-N-methylaniline is the optimal allylamine. The cyclization products were obtained in yields ranging from 16% to 96%. The reaction does not require an external oxidant, and a possible mechanism is proposed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: The [Ru(p-cymene)Cl-2](2)-catalyzed reaction of 2-arylpyridines with 1-aryl-2-vinylpyrrolidines in CF3CH2OH at 40 ? in the presence of KOAc affords ortho-C-H allylation products of arenes with high yields and Z/E ratios. The protocol is applicable to a wide range of substrates and tolerates various functional groups including alkyl, aryl, MeO, F, Cl, Br, OCF3, and CF3 groups.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: Alkyl aryl ketones were synthesized through a nickel-catalyzed reductive coupling reaction of arylcarboxylic acid (2-pyridyl)esters with alkyl methanesulfonates, both primary and secondary, under mild conditions. This methodology is compatible with various substrates and functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Yu-Tong Duan, Zhong-Xia Wang
Summary: The ruthenium-catalyzed reaction of aryl methyl thioethers with vinylaziridines provides ortho-position mono- or bis-allylation products, depending on the substituents on the phenyl rings of sulfide substrates or the ratio of reactants. This reaction exhibits mild conditions, high product yields, a broad range of substrates, good compatibility of functional groups, and selective formation of E-configurated C-C double bonds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: The nickel-catalyzed cross-electrophile coupling of aryl chlorides with allylic alcohols proceeds efficiently under mild conditions in the presence of zinc powder and MgCl2 to produce allylarenes in moderate to high yields. The reaction exhibits high regioselectivity and E/Z-selectivity, particularly when 1- or 3-arylallyl alcohols are used as substrates. Various functional groups and nitrogen-containing heterocycles are tolerated in the reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xue-Yi He, Zhong-Xia Wang
Summary: The synthesis of 1,4-enynes via nickel-catalyzed cross-coupling of allylic alcohols with alkynylzinc reagents exhibits high regio- and E/Z-selectivity, especially when aryl-substituted allylic alcohols are employed. The method also shows a wide scope of substrates and good compatibility of functional groups.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Wei-Ze Li, Zhong-Xia Wang
Summary: The Ni(PEt3)Cl-2-catalyzed silylation of alkyl aryl sulfoxides with silylzinc reagents allows for the conversion to arylsilicon compounds under mild reaction conditions, with tolerance to a variety of functional groups and a wide scope of substrates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Wei-Ze Li, Zhong-Xia Wang
Summary: The alpha-alkylation of methyldiarylphosphine oxides with (hetero)arylmethyl alcohols was successfully achieved under nickel catalysis, yielding 30-90% of the desired products. Various arylmethyl and heteroarylmethyl alcohols can be utilized and functional groups on the aromatic rings are well tolerated, making it a versatile transformation. The reaction conditions are also applicable for the alpha-alkylation of dialkyl methylphosphonates.
ORGANIC & BIOMOLECULAR 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.
