Article
Chemistry, Organic
Lei Dai, Zhou Zhang, Guangzhou Zhu, Yun Liu, Xiaoqin Liu, Jinpeng Zhang, Liangce Rong
Summary: This article describes the Selectfluor-promoted vicinal fluorohydroxylation and hydration reaction of para-quinone methides (p-QMs), which affords vicinal fluorohydrins and ketone/ether products in high yields. The electronic properties of substituents in the aromatic ring highly control the hydration products, and the amount of Selectfluor is significantly different during the synthesis of ketone/ether products. This reaction also marks the first fluorohydroxylation of p-QMs, and the wide range of p-QMs makes the vicinal fluorohydroxylation of great significance.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xiao-Yue Chen, Ya-Ning Li, Yichen Wu, Jiahui Bai, Yinlong Guo, Peng Wang
Summary: The development of novel and reactive linchpins for carbon-carbon and carbon-heteroatom bond formation reactions has greatly contributed to the success of synthetic chemistry. This study reports the efficient synthesis of aryl sulfonium salts, a versatile electrophilic linchpin, through a novel Cu-mediated thianthrenation and phenoxathiination. Furthermore, the formal thianthrenation of arenes is achieved through the sequential Ir-catalyzed C-H borylation and Cu-mediated thianthrenation, providing a complementary method for late-stage functionalization of pharmaceuticals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Multidisciplinary
Miha Ravbar, Amadeja Koler, Muzafera Paljevac, Mitja Kolar, Peter Krajnc, Jernej Iskra
Summary: In this study, palladium was immobilized on a highly porous copolymer to obtain a supported catalyst with good catalytic activity and recyclability. The immobilized catalyst was able to catalyze the coupling reaction at room temperature and tolerated various substituents on the aromatic ring.
Article
Chemistry, Organic
Steve Karreman, Simon B. H. Karnbrock, Sebastian Kolle, Christopher Golz, Manuel Alcarazo
Summary: The synthesis of S-aryl dibenzothiophenium salts and their transformation into 6H-benzo[c]chromenes is achieved through a highly selective reaction pathway, involving photocatalytic single-electron transfer and cyclization of radical intermediates. The mechanistic studies reveal a kinetically favored cyclization pathway and subsequent ring expansion towards the desired tricyclic systems.
Article
Biochemistry & Molecular Biology
Satenik Mkrtchyan, Michal Jakubczyk, Suneel Lanka, Michael Pittelkow, Viktor O. Iaroshenko
Summary: A synthetic methodology using copper-catalyzed direct arylation was developed for the preparation of aromatic amides from 2-bromo-2,2-difluoroacetamides. The reactions were efficient and successful with aryl groups of various electronic natures, allowing for the rapid preparation of diverse aromatic amides.
Article
Chemistry, Organic
Gangqi Peng, Hao Cheng, Xiya Cheng, Yang He, Yuanyuan An, Jie Wu, Danqing Zheng
Summary: A reductive Sandmeyer-type sulfinylation reaction of aryldiazonium salts with sodium sulfinates was developed, which proceeds under photocatalysis and generates various sulfoxides of significant value via radical substitution pathway. The in situ diazotization of aromatic amines in a one-pot, two-step process also allows for the conversion to corresponding sulfoxides. The successful late-stage sulfinylation of drug-based amines further demonstrates the practicality of this method.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Organic
Qing-Zhu Li, Wen-Lin Zou, Zhi-Qiang Jia, Jun-Long Li
Summary: Allyl and propargyl sulfonium salts have emerged as versatile building blocks for the assembly of cyclic skeletons, offering diverse nucleophilic or electrophilic reactive positions for annulation reactions. This growing field presents a comprehensive overview of recent developments and various annulation reactions involving allyl and propargyl sulfonium salts.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Weiwei Yao, Kang Lv, Zixi Xie, Hui Qiu, Mengtao Ma
Summary: A simple and efficient electrochemical sulfonylation reaction has been reported for the first time. Various aryl, heteroaryl, and alkenyl sulfones were obtained in good yields using sodium arylsulfinate salts in a catalyst-free and additive-free system. The proposed mechanism is based on radical-trapping and CV control experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Che-Ming Hsu, Shao-Chi Lee, Hao-En Tsai, Yong-Ting Tsao, Cheng-Lin Chan, Shinje Minoza, Zong-Nan Tsai, Li-Yun Li, Hsuan-Hung Liao
Summary: In this study, we successfully activated the C-S bond in sp(3)-hybridized thiols by introducing a per-/polyfluoroaryl moiety, enabling the efficient removal of sulfur groups and the generation of aliphatic radicals that can react with aryl halides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yushan Xiao, Yimin Jia, Jinfeng Huang, Xiangyu Li, Zhiwen Zhou, Jing Zhang, Mou Jiang, Xin Zhou, Zhong-Xing Jiang, Zhigang Yang
Summary: A metal-free direct trifluoromethylthiolation method has been established for the synthesis of SCF3-substituted sulfonium ylides, using sulfonium salt or alpha-bromoacetic ester as precursors. This method enables the construction of SCF3-substituted sulfonium ylides from a wide range of substrates, including ketones, esters, and PEGylated substrates. The application of this approach in large-scale preparation and the fluorescence and fluorine-19 magnetic resonance imaging capabilities of the product are also explored.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ignacio Medina-Mercado Susana Porcel
Summary: A gold-catalysed coupling reaction between aryldiazonium salts and arylboronic acids is described. The reaction proceeds efficiently under blue LED irradiation in the presence of KF and a catalytic amount of ascorbic acid, yielding satisfactory results. Notably, 4-nitrobenzendiazonium tetrafluoroborate exhibits sufficient reactivity to undergo the coupling reaction with various arylboronic acids even in the absence of aryl radical initiators. This coupling reaction is applicable for substrates with electron-donating and electron-withdrawing groups at the para, ortho, and meta positions.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Fabio Julia, Jiyao Yan, Fritz Paulus, Tobias Ritter
Summary: A vinyl thianthrenium salt has been introduced as an effective vinylating reagent, which can be readily prepared from ethylene gas and is broadly useful in various annulation chemistry reactions. Its unique structural features enable a distinct synthesis and reactivity profile, unprecedented for other vinyl sulfonium derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Zhen-Hua Wang, Tong Zhang, Qing-Fei Yan, Jian-Qiang Zhao, Yong You, Yan-Ping Zhang, Jun-Qing Yin, Wei-Cheng Yuan
Summary: In this article, various α-aryl vinylsulfonium salts were successfully transformed under mild reaction conditions, leading to the synthesis of diverse 1,2-dihydroquinoline and ring-fused tetrahydroquinoline skeletons with moderate to excellent yields. The potential application of the method was demonstrated by scale-up experiments and further derivatizations of the products. The developed protocol offers mild and transition-metal-free reaction conditions, along with easy operation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Engineering, Chemical
Laura Adarve-Cardona, Diego Gamba-Sanchez
Summary: In this manuscript, we describe a method for reducing sulfoxides using ethyl vinyl ether/oxalyl chloride. The reaction involves the formation of chlorosulfonium salts, which are highly electrophilic and react with the sulfoxide. The nucleophilic vinyl ether then scavenges the chlorine, resulting in the formation of the corresponding sulfide. This method is suitable for large-scale applications and can be used with highly functionalized sulfoxides. Chromatographic purification is only necessary in special cases, and the final product can usually be obtained by simple evaporation.
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Organic
Zhou-Zhou Han, Cheng-Pan Zhang
Summary: A catalyst- and additive-free ring-opening polymerization of tetrahydrofuran initiated by phenyl(trifluoroethyl)iodonium triflate was developed without the need for photo-irradiation. The reaction produced CF3CH2-terminated polytetrahydrofuran in good yields and with different Mn-(NMR) values under room temperature or elevated temperature. This method provided a novel synthetic route to polytetrahydrofuran bearing a trifluoroethyl end group.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Xiao-Xia Ming, Shuai Wu, Ze-Yu Tian, Jia-Wei Song, Cheng-Pan Zhang
Summary: The study confirmed the potential of (2-bromoethyl)diphenylsulfonium triflate as a powerful vinylation reagent in Sonogashira cross-coupling reactions. The vinylation proceeded smoothly at 25 degrees C under Pd/Cu catalysis, yielding a variety of 1- and 2-unsubstituted 1,3-enynes in moderate to excellent yields. This protocol represents the first application of (2-haloethyl)diphenylsulfonium triflate as a CH=CH2 transfer source in organic synthesis.
Article
Chemistry, Organic
Yu Ma, Ze-Yu Tian, Shuang-Yang Zheng, Cheng-Pan Zhang
Summary: Cyclopropyldiphenylsulfonium salt has been successfully used as an efficient allylation reagent in copper-catalyzed reactions with amines, providing N-allylated products in good yields. The method shows good functional group tolerance and excellent chemoselectivity, and offers an interesting approach for the synthesis of N-allyl amines.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Organic
Ze-Yu Tian, Yu Ma, Cheng-Pan Zhang
Summary: The application of alkylsulfonium salts as alkyl-transfer reagents in organic synthesis has reemerged. They can readily alkylate various nucleophiles, alkenes, arenes, alkynes, organometallic reagents, etc., and offer convenience, high efficiency, readily accessible and structurally diversified alkylation reagents, good functional group tolerance, and a wide range of substrate types.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Long-Yu Ran, Xue Ding, Xue-Ping Yan, Cheng-Pan Zhang
Summary: This article describes the synthesis of alkyl fluorides and carbonates via divergent dehydroxyfluorination and carbonation of alcohols with trifluoromethyl trifluoromethanesulfonate (CF3SO2OCF3). Reactions with BTMG in THF yielded alkyl fluorides in good yields, while reactions of two different alcohols with Et3N in DCM formed asymmetric carbonates in moderate to excellent yields. CF3SO2OCF3 was shown to serve as either a F or a CO reagent in the reactions by changing the base, enabling the selective construction of alkyl fluorides and carbonates with high efficiency. Notably, the synthesis of fluorine-containing asymmetric carbonates, which are difficult to prepare by other methods, was comprehensively achieved by this method, demonstrating its significant application potential in both academia and industry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Zeng-Hui Lin, Yu-Fei Yao, Cheng-Pan Zhang
Summary: Deuteration of arylthianthren-S-ium triflates with CD3OD or CD3OD/CD3COCD3 in the presence of Cs2CO3 by palladium catalysis or photoirradiation allows for the convenient synthesis of deuterated arenes in good yields. The Pd-catalyzed reaction generally gives better yields than the photoinduced deuteration, but exceptions exist. These reactions highlight eco-friendly conditions, simplicity, inexpensive deuterium sources, good functional group tolerance, and a range of substrates. This protocol provides a high selectively formal aromatic C-H deuteration for efficient deuterium labeling of multifunctionalized arenes and drug molecules.
Article
Multidisciplinary Sciences
Jing-Yan Dong, Hao-Nan Wang, Yan-Qian Xie, Cheng-Pan Zhang
Summary: This study presents a copper-mediated trifluoromethyltelluration reaction of arylboronic acids with [Me4N][TeCF3], using air as an environmentally friendly oxidant. The reaction proceeds smoothly under mild conditions, providing the corresponding trifluoromethyltellurated products in good yields. This method offers a convenient access to various TeCF3-containing molecules.
Review
Chemistry, Multidisciplinary
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: This review summarizes the advances in the synthesis and typical applications of carbamoyl fluorides, fluoroformates, and their analogues since 1980. It focuses on the use of O/S/Se=CF2 species or their equivalents as fluorocarbonylation reagents for the direct construction of these compounds from parent heteroatom-nucleophiles.
Article
Chemistry, Organic
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: Visible-light-induced decarboxylative trifluoromethylselenolation of (hetero)aromatic carboxylic acids with [Me4N][SeCF3], oxidant, and catalysts leads to the synthesis of various (hetero)aryltrifluoromethyl selenoethers in good yields. The reaction proceeds via a radical process involving oxidative decarboxylation of the carboxylic acids using NFSI as the oxidant, [di-tBu-Mes-Acr-Ph][BF4] as the photocatalyst, and 1,1'-biphenyl as the cocatalyst. The presence of copper salts enhances the trifluoromethyl selenoethers formation through Cu-mediated cross-coupling reactions. This protocol offers advantages such as visible light irradiation, mild reaction conditions, good functional group tolerance, and applicability to drug molecules, overcoming the limitations of known trifluoromethylselenolation methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fei Li, Xue Han, Ziang Xu, Cheng-Pan Zhang
Summary: This study presents a visible-light-induced metal-free trifluoromethylselenolation reaction of aryl iodides and bromides with [Me4N][SeCF3]. The reaction was carried out at ambient temperature by utilizing a light-sensitive SeCF3 reagent. Mechanistically, EDA complexes between aryl halides and the -SeCF3 anion or the base could be formed and excited by light, leading to intracomplex single-electron transfer (SET) processes that generate aryl and center dot SeCF3 radicals as crucial intermediates, enabling a convenient and environmentally friendly approach to various aryl trifluoromethyl selenoethers.
Article
Chemistry, Multidisciplinary
Jing-Yan Dong, Hao-Nan Wang, Cheng-Pan Zhang
Summary: Metal-free trifluoromethyltellurolation of indoles was achieved using [Me4N][TeCF3] as a reagent in the presence of NIS, resulting in the synthesis of 3-TeCF3-substituted indole derivatives in high yields. The reaction displayed good functional group tolerance and proceeded smoothly under mild conditions. It is noteworthy that [Me4N][TeCF3] exhibited distinct reactivity compared to [Me4N][SeCF3] in indole systems.
Article
Chemistry, Multidisciplinary
Lei Liu, Yu-Cheng Gu, Cheng-Pan Zhang
Summary: The trifluoromethylselenolation of arenes through Pd-catalyzed C(sp(2))-H activation with the assistance of a directing group and an oxidant has been established for the first time. This reaction tolerates various directing groups and functional groups, allowing selective installation of a SeCF3 moiety onto the ortho positions of arenes. Mechanistic studies suggest that the CF3SeSeCF3 intermediate generated in situ from the oxidation of [Me4N][SeCF3] may be the actual SeCF3 reagent in the reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ze-Yu Tian, Cheng-Pan Zhang
Summary: This study reported an efficient visible-light-induced cross-coupling reaction of arylsulfonium triflate with [Me4N][SeCF3] for the synthesis of various aryl trifluoromethyl selenoethers. The reaction exhibits operational simplicity, high efficiency, catalyst- and additive-free conditions, wide substrate scope, and good yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Lei Liu, Long-Yu Ran, Yucheng Gu, Cheng-Pan Zhang
Summary: Tetramethylammonium trifluoromethylselenate has been confirmed as an excellent precursor for selenofluorophosgene, allowing for the preparation of selenocarbamoyl fluorides, selenoureas, and heterocycles without the need for catalysts or additives. The reactions with different types of amines result in the formation of a variety of selenium-containing compounds.
ORGANIC CHEMISTRY FRONTIERS
(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.
