Article
Chemistry, Organic
Wei-Sian Li, Ting-Shen Kuo, Ping-Yu Wu, Chien-Tien Chen, Hsyueh-Liang Wu
Summary: The direct asymmetric synthesis of 1-aryl tetrahydroisoquinolines utilizing 3,4-dihydroisoquinolinium tetraarylborates is reported in this study. The dual roles of anionic tetraarylborates enable the convergent synthesis of enantioenriched 1-aryl THIQs in good yields with high enantioselectivity, as demonstrated by the formal synthesis of (-)-solifenacin and (-)-Cryptostyline I.
Article
Chemistry, Multidisciplinary
Shubhendu S. Karandikar, Avik Bhattacharjee, Bryan E. Metze, Nicole Javaly, Edward J. Valente, Theresa M. McCormick, David R. Stuart
Summary: Diarylhalonium compounds play important roles as reagents and catalysts in organic synthesis, with the key reactivity of the three center, four electron bond requiring refinement for broader applicability. The combination of Density Functional Theory, Natural Bond Orbital Theory, and X-ray structure data can provide insights into the bonding and structure of these compounds.
Article
Chemistry, Multidisciplinary
Yun Ye, Jie Zhu, Haijiao Xie, Yinhua Huang
Summary: A ligand-controlled rhodium-catalyzed reaction has been reported, which allows the synthesis of different structures of alkene products in a switchable manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Matteo Lanzi, Torben Rogge, Tan Sang Truong, K. N. Houk, Joanna Wencel-Delord
Summary: Hypervalent chloranes are rare and poorly explored reagents that possess unique electronic properties. This study reports highly chemo- and regioselective, metal-free, and mild C-C and C-O couplings using these chloranes. Mechanistic studies reveal the unprecedented reactivities and selectivities of these systems and the involvement of aryne intermediates. The synthetic potential of these transformations is demonstrated through post-functionalization of the coupling products obtained from chloranes and phenols under different conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yiwen Wang, Ya-Nan Tian, Shiyan Ren, Ruijie Zhu, Bin Huang, Yanqiong Wen, Shiqing Li
Summary: The homo anion-cation coupling of cyclic diaryl lambda(3)-bromanes/diarylbrominiums is reported for the first time, which has not been previously reported. Competition experiments indicate that the anion-cation coupling follows the nucleophilic ability of the anions, with higher nucleophilicity resulting in higher reactivity. Additionally, a metal-free cross-coupling reaction of cyclic diarylbrominium tosylates with various alcohols, phenols, water, and their deuterated forms has been developed under mild conditions, yielding meta-functionalized biaryl motifs in high yields with broad substrate scope. Preliminary mechanistic studies suggest that the nucleophilic agent is the main source of protons in the cross-anion-cation coupling, which is influenced by its concentration.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Daichi Ikeshita, Hiroki Shimura, Sho Miyakawa, Yusuke Masuda, Naoki Ishida, Masahiro Murakami
Summary: In this study, we demonstrate that the onium salt-forming reaction of triarylphosphines with aryl bromides can be efficiently promoted by the sequential cooperation of light with palladium. The reaction conditions are mild and tolerant of various functional groups such as amino and hydroxy groups, providing a convenient and expedient access to variously substituted tetraarylphosphonium salts.
Review
Chemistry, Multidisciplinary
Binlin Zhao, Baskaran Prabagar, Zhuangzhi Shi
Summary: C-H functionalization is a fast and atom-economical approach for synthesizing complex molecules, beneficial for late-stage modifications. Modern strategies allow cleavage of less reactive bonds to form essential links, highlighting renewable and sustainable features.
Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Aleksandra Nilova, Bryan Metze, David R. Stuart
Summary: Controlling reaction pathways selectively leads to a broad scope of arenes and arynophiles, offering efficient access to diverse arene chemical space and biologically active compounds with high yields.
Article
Chemistry, Multidisciplinary
Yuan Cai, Tobias Ritter
Summary: This study presents a photocatalyzed Meerwein-type bromoarylation of alkenes using stable arylthianthrenium salts, which are formed through site-selective C-H thianthrenation. This method allows for late-stage functionalization of biomolecules that are typically inaccessible with other aryl coupling reagents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Natalia S. Soldatova, Artem V. Semenov, Kirill K. Geyl, Sergey V. Baykov, Anton A. Shetnev, Anna S. Konstantinova, Mikhail M. Korsakov, Mekhman S. Yusubov, Pavel S. Postnikov
Summary: A method for copper-catalyzed N-arylation of diverse oxadiazolones using diaryliodonium salts has been reported with high yields up to 92%. It was found that the steric effects in aryl moieties determined the chemoselectivity of arylations. Mesityl-substituted diaryliodonium salts demonstrated high potential as selective arylation reagents.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Katherine Townsend, Malcolm P. Huestis, John C. Tellis
Summary: A method for the cross-coupling of S-aryl and S-alkyl potassium thiomethyltrifluoroborates with aryl and heteroaryl bromides is reported using photoredox/nickel dual catalysis. The reaction proceeds under mild conditions, providing benzylthioether products in moderate to good yields with good functional group tolerance. Additionally, a practical and improved synthesis of potassium thiomethyltrifluoroborates is described, offering access to previously undescribed reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Na-Na Ma, Jing-Ao Ren, Xiang Liu, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: The direct cross-couplings of aryl sulfonium salts with aryl halides using nickel as a reaction catalyst were successfully achieved. The reactions proceeded efficiently via C-S bond activation at ambient temperature, providing moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions.
Article
Chemistry, Organic
Fathima Pilathottathil, Sreelakshmi Unnikrishnan, Tamilarasu Murugesan, Alagiri Kaliyamoorthy
Summary: In this study, a synthetic strategy for direct trideuteromethylation of sulfenate ions derived from beta-sulfinyl esters in the presence of a base using CD3OTs was developed. The method allows for the straightforward synthesis of trideuteromethyl sulfoxides with high yields and deuteration levels. The resulting trideuteromethyl sulfoxide can be easily modified into trideuteromethyl sulfone and sulfoximine.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Vaibhav Pramod Charpe, Ayyakkannu Ragupathi, Arunachalam Sagadevan, Kuo Chu Hwang
Summary: The study has developed a visible light-induced photo-redox copper-catalyzed method for the synthesis of functionalized quinazolines at room temperature, which is suitable for anti-cancer drug synthesis, and has environmental friendliness and feasibility demonstrated through green chemistry metrics and evaluations.
Article
Chemistry, Organic
Min Zhang, Jin-Hong Lin, Ji-Chang Xiao
Summary: The efficient construction of HCF2Se and HCF2S groups is achieved through tandem substitutions between alkyl bromides and a reagent system consisting of MSeCN (or MSCN) and Ph3P+CF2H Br-. The tandem process involves the first nucleophilic substitution of alkyl bromides by -SeCN (or -SCN) followed by nucleophilic difluoromethylation.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Min Zhang, Jin-Hong Lin, Ji-Chang Xiao
Summary: TFSP, an efficient trifluoromethylation reagent, can be readily prepared from cheap industrial feedstocks, enabling effective trifluoromethylation reactions of alkenes under photocatalysis.
Article
Chemistry, Organic
Yijie Hu, Xiaoli Wang, Nan Ren, Na Li, Jianyang Li, Jie Chen, Hui Zhang, Hongmei Deng, Weiguo Cao, Jin-Hong Lin
Summary: This study presents the first synthesis of fluoroalkylated benzimidazole- or indole-fused benzoxazines using fluoroalkylated propiolates as building blocks. The reactions proceeded smoothly under mild conditions, giving the desired products in moderate to high yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yi-Fei Yang, Jin-Hong Lin, Ji-Chang Xiao
Summary: This study presents a general method for the hydrotrifluoromethylation of styrene under photoredox catalysis using a newly developed trifluoromethylation reagent, TFSP. The substrate scope was further expanded to include unactivated alkenes, acrylates, acrylamides, and vinyl-heteroatom-substituted alkenes, demonstrating the tunability of this method.
Article
Chemistry, Organic
Fang Xiao, Jin-Hong Lin, Fei Hao, Xing Zheng, Yu Guo, Ji-Chang Xiao
Summary: A protocol for visible light mediated C-H trifluoromethylation of unactivated (hetero)arenes under blue LED irradiation has been developed. It enables the rapid construction of a range of CF3-containing (hetero)arenes in moderate to high yields from the readily accessible trifluoromethylsulfonyl-pyridinium salt (TFSP). This protocol is also suitable for nitrogen-containing aromatic heterocycles, which are potentially useful in medicinal chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Bai-Yu Qian, Wei Zhang, Jin-Hong Lin, Weiguo Cao, Ji-Chang Xiao
Summary: In this paper, a convenient anti-Markovnikov iodofluorination of alkenes was described using Selectfluor/(Bu4NI)-Bu-n as the reagent. The reaction showed a broad substrate scope, good functional group tolerance, and the ability to construct various C-F bonds.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Wei Zhang, Xiaoyun Deng, Feng-Xu Zhang, Jin-Hong Lin, Ji-Chang Xiao, Steven H. Liang
Summary: This study discovered the unusual reactivity of the SO2OCF2H group and successfully developed a synthetic tool for well-functionalized alkenyl sulfonyl fluorides, as well as achieving the first 18F labeling of alkenyl sulfonyl fluorides.
Article
Chemistry, Organic
Feng-Xu Zhang, Jin-Hong Lin, Ji-Chang Xiao
Summary: Here, we report the design and synthesis of a difluoromethylsulfonyl imidazolium salt, which serves as a radical difluoromethylation reagent for achieving amino- and oxy-difluoromethylation of alkenes. Importantly, the synthesis of the imidazolium salt can be accomplished without the need for distillation or column chromatography purification, and the amino- and oxy-difluoromethylation pathways are determined by the choice of reaction solvents.
Article
Chemistry, Organic
Yi-Jun Xiang, Shun Liu, Jing Zhou, Jin-Hong Lin, Xu Yao, Ji-Chang Xiao
Summary: Described here is a dehydroxylative sulfonylation method using R3P/ICH2CH2I as a promoter to convert alcohols into sulfonyl compounds. Unlike previous methods that are limited to active alcohols, our protocol can be applied to both active and inactive alcohols (alkyl alcohols). Various sulfonyl groups, including CF3SO2 and HCF2SO2, can be incorporated, which are of interest in pharmaceutical chemistry. The reaction is completed within 15 minutes, and the reagents used are cheap and readily available.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ling-Ying Chen, Peng-Fei Pan, Jin-Hong Lin, Chuan-Ming Jin, Ji-Chang Xiao
Summary: This paper describes a convenient synthesis of an efficient trifluoromethoxylation reagent, C4F9SO3CF3, using cheap and widely available reagents, and without the need for any tedious column chromatography purification procedure.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wen-Jie Pan, Jiao Yu, Wei-Guo Cao, Ji-Chang Xiao, Jin-Hong Lin
Summary: Difluorocarbene has been used as a versatile intermediate for incorporating fluorinated groups into organic molecules. In this study, it was revealed that difluorocarbene can function as a C-F source for the synthesis of fluorinated benzothiazoles, which may have potential applications in drug development.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Wei-Ying Tang, Xing Zheng, Xu Yao, Jin-Hong Lin, Qu-Tong Zheng, Ji-Chang Xiao
Summary: Due to the widespread occurrence of hydroxyl groups, the reductive deoxygenation of alcohols is an active research area. This study presents a new efficient method using Ph3P/ICH2CH2I and NaBH4, which has a wide substrate scope, good functional group tolerance, and convenient operation with low reagent cost.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wei Zhou, Wen-Jie Pan, Jie Chen, Min Zhang, Jin-Hong Lin, Weiguo Cao, Ji-Chang Xiao
Summary: This article reviews recent progress in the transfer of transition-metal difluorocarbenes and their reactivities, providing insights that may aid in the design of catalytic transfer of difluorocarbene for various reactions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fei Hao, Xueyun Shang, Zhenwei Liu, He Zhang, Jin-Hong Lin, Ji-Chang Xiao
Summary: A Rh-catalyzed tunable defluorinative borylation method was developed to provide high Z/E selectivities for allylborylated monofluoroalkenes or homoallylborylated monofluoroalkenes. Different reaction paths were observed with slight changes in reaction conditions, and the allylborylated monofluoroalkenes could be further converted into dihydroxyl-containing monofluoroalkenes.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Min Zhang, Jin-Hong Lin, Chuan-Ming Jin, Ji-Chang Xiao
Summary: The study presents a Cu-catalyzed reaction that does not require toxic cyanation reagents, using BrCF2CO2Et and NH4HCO3 under photocatalytic conditions to achieve the cyanodifluoromethylation of alkenes. The Cu-complex serves as both a photocatalyst and a coupling catalyst for the formation of a C-CN bond.
CHEMICAL COMMUNICATIONS
(2021)