摘要：
A mild strategy for the synthesis of boron‐handled pyrazoles through photocatalytic cascade radical cyclization of LBRs (Lewis base‐boryl radicals) with vinyldiazo reagents is described here. The reaction starts with the addition of LBRs at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Abstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base–boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research.
摘要：
In an effort to make pesticide use safer, more efficient, and sustainable, micro-/nanocarriers are increasingly being utilized in agriculture to deliver pesticide-active agents, thereby reducing quantities and improving effectiveness. In the use of nanopesticides, the choice to further design and prepare pesticide stimulus-responsive nanocarriers based on changes in the plant growth environment (light, temperature, pH, enzymes, etc.) has received more and more attention from researchers. Based on this, this paper examines recent advancements in nanomaterials for the design of stimulus-responsive micro-/nanocarriers. It delves into the intricacies of preparation methods, material enhancements, in vivo/ex vivo controlled release, and application techniques for controlled release formulations. The aim is to provide a crucial reference for harnessing nanotechnology to pursue reduced pesticide use and increased efficiency.
摘要：
The development of efficient, bright, and stable narrowband light-emitting electrochemical cells (LECs) has remained a challenge. Here, intrinsically ionic multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters are reported as guest emitters for narrowband LECs, which are developed by attaching an imidazolium cation onto a typical MR-TADF emitter. In solution, the emitters show green-blue emission peaked at 486-497 nm with small full widths at half-maximum (FWHMs) at 24-26 nm. In doped films, they show narrowband green-blue emission with high luminescent efficiencies at approximate to 90%. LECs using an ionic exciplex host and the ionic MR-TADF guest emitters show green-blue emission peaked at 494-503 nm with small FWHMs at 31-34 nm, and afford high external quantum efficiencies (EQEs) up to 10% under constant-voltage driving. With ionic TADF small-molecule hosts, the narrowband LECs show high EQEs up to 13.0% under constant-voltage driving, which is the highest among all reported narrowband LECs, and afford peak brightness/EQE/half lifetime at 780 cd m-2/5.6%/62.2 h under constant-current driving. A long half-lifetime of approximate to 630 h has further been achieved at 136 cd m-2. The work demonstrates the great potential for the use of intrinsically ionic MR-TADF guest emitters and ionic TADF hosts to develop efficient, bright, and stable narrowband LECs. Narrowband light-emitting electrochemical cells (LECs) are fabricated with ionic multi-resonance thermally- activated delayed fluorescence (TADF) guest emitters, which show high external quantum efficiencies (EQEs) up to 13.0% under constant-voltage driving and peak brightness/EQE/half-lifetime at 780 cd m-2/5.6%/62.2 h under constant-current driving. A half-lifetime of approximate to 630 h is further achieved at 136 cd m-2. image
期刊：
Highlights in Chemical Science,2024年15(14):5061-5081 ISSN：2041-580X
通讯作者：
Luo, Zhu;Guo, YB
作者机构：
[Guo, YB; Qiu, Xiaofeng; Luo, Zhu; Wu, Yan; Guo, Yanbing; Zhang, Shuhong; Zhu, Yuhua; Hao, Quanguo] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430082, Hubei, Peoples R China.;[Guo, YB; Luo, Zhu; Guo, Yanbing] Wuhan Inst Photochem & Technol, 7 North Bingang Rd, Wuhan 430082, Hubei, Peoples R China.;[Zhu, Yuhua] Wuhan Univ, Sch Civil Engn, Wuhan 430072, Peoples R China.
通讯机构：
[Guo, YB ; Luo, Z] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430082, Hubei, Peoples R China.;Wuhan Inst Photochem & Technol, 7 North Bingang Rd, Wuhan 430082, Hubei, Peoples R China.
摘要：
Graphdiyne (GDY)-based materials, owing to their unique structure and tunable electronic properties, exhibit great potential in the fields of catalysis, energy, environmental science, and beyond. In particular, GDY/metal oxide hybrid materials (GDY/MOs) have attracted extensive attention in energy and environmental catalysis. The interaction between GDY and metal oxides can increase the number of intrinsic active sites, facilitate charge transfer, and regulate the adsorption and desorption of intermediate species. In this review, we summarize the structure, synthesis, advanced characterization, small molecule activation mechanism and applications of GDY/MOs in energy conversion and environmental remediation. The intrinsic structure-activity relationship and corresponding reaction mechanism are highlighted. In particular, the activation mechanisms of reactant molecules (H2O, O2, N2, etc.) on GDY/MOs are systemically discussed. Finally, we outline some new perspectives of opportunities and challenges in developing GDY/MOs for efficient energy and environmental catalysis. This review summarizes the structure, synthesis, advanced characterization, structure-activity relationship, and mechanisms of graphdiyne/metal oxide hybrid materials in efficient energy and environmental catalysis.
摘要：
In the pursuit of advancing materials for methane storage, a critical consideration arises given the prominence of natural gas (NG) as a clean transportation fuel, which holds substantial potential for alleviating the strain on both energy resources and the environment in the forthcoming decade. In this context, a novel approach is undertaken, employing the rigid triptycene as a foundational building block. This strategy is coupled with the incorporation of dichloromethane and 1,3-dichloropropane, serving as rigid and flexible linkers, respectively. This combination not only enables cost-effective fabrication but also expedites the creation of two distinct triptycene-based hypercrosslinked polymers (HCPs), identified as PTN-70 and PTN-71. Surprisingly, despite PTN-71 manifesting an inferior Brunauer-Emmett-Teller (BET) surface area when compared to the rigidly linked PTN-70, it showcases remarkably enhanced methane adsorption capabilities, particularly under high-pressure conditions. At a temperature of 275 K and a pressure of 95 bars, PTN-71 demonstrates an impressive methane adsorption capacity of 329 cm(3) g(-1). This exceptional performance is attributed to the unique flexible network structure of PTN-71, which exhibits a pronounced swelling response when subjected to elevated pressure conditions, thus elucidating its superior methane adsorption characteristics. The development of these advanced materials not only signifies a significant stride in the realm of methane storage but also underscores the importance of tailoring the structural attributes of hypercrosslinked polymers for optimized gas adsorption performance.
摘要：
Trichloroethylene (TCE) with trace concentrations is often detected in soils and groundwater, posing potential damages to public health. The elimination of TCE can be achieved through reductive dechlorination using zero-valent iron (ZVI). However, ZVI usually suffers from the presence of passive iron (hydro)oxides layer and low electron transfer rate, thus leading to the unsatisfactory reactivity. Herein, we fabricated oxalated ZVI (Ox-ZVI(bm)) by mechanical ball-milling of micro-scale ZVI and H2C2O4 center dot 2H(2)O to modify the ZVI surface composition. To be specific, the modification of the iron oxide shell by oxalic acid facilitated the generation of unsaturated coordination Fe(II), enhancing TCE adsorption. Furthermore, the formed FeC2O4 on the iron oxide shell improved electron transfer efficiency, contributing to the enhanced TCE reductive dechlorination. Impressively, the rate of TCE degradation by Ox-ZVI(bm) was 10-fold higher than that of ZVI(bm) without oxalate modification. Moreover, Ox-ZVI(bm) samples were filled in a laboratory Permeable Reactive Barriers (PRB) column to treat actual underground wastewater containing TCE pollutants. The effluent concentration of TCE maintained steadily below 0.21 mg/L for over 10 days, complying with the National Groundwater Class IV standard (GBT 14848-2017). This marks a significant step toward practical groundwater treatment.
期刊：
JOURNAL OF NATURAL PRODUCTS,2024年87(1):141-151 ISSN：0163-3864
通讯作者：
Ruan, HL
作者机构：
[Ruan, Han-Li; Hu, Jia-Yun; Qin, Chun-Lun; Chang, Jin-Ling; Pei, Jiao; Ouyang, Qian-Xi; Ruan, HL; Zhou, Yin-Hui] Huazhong Univ Sci & Technol, Tongji Med Coll, Sch Pharm, Hubei Key Lab Nat Med Chem & Resource Evaluat, Wuhan 430030, Peoples R China.;[Meng, Xiang-Gao] Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.
通讯机构：
[Ruan, HL ] H;Huazhong Univ Sci & Technol, Tongji Med Coll, Sch Pharm, Hubei Key Lab Nat Med Chem & Resource Evaluat, Wuhan 430030, Peoples R China.
摘要：
Twelve new austalide meroterpenoids (1-12) were isolated from the endophytic fungus Diaporthe sp. XC1211. Their structures were elucidated by extensive spectroscopic analysis. The absolute configurations of compounds 1, 3, 4, and 6 were established by single-crystal X-ray diffraction, whereas those for the others were established by experimental electronic circular dichroism (ECD) data analysis. Compounds 1-12 represent a rare class of austalides with a 24α-CH(3). Compounds 2 and 5 demonstrated potent proliferation inhibitory effects against LPS-induced B cells with IC(50) values of 6.7 (SI = 3.6) and 3.8 (SI > 13) μM, respectively. Compounds 2 and 5 decreased the secretion of IL-6 in LPS-induced B cells in a dose-dependent manner.
摘要：
Two new Zn(II)/Cd(II) luminescent coordination polymers (CPs) based on the V-shaped bis(imidazole) ligand 3,6-bis (1H-benzo[d]imidazol-1-yl)-9-methyl-9H-carbazole (bbimc) with [1,1'-biphenyl]-4,4'-dicarboxylic acid ligand (H(2)bpdc) have been synthesized under solvothermal conditions: {[Zn(bbimc)(bpdc)]·DMF·2.5H(2)O} (CP 1), {[Cd(bbimc)(bpdc)]·2DMF} (CP 2). CP 1 and CP 2 both display a uninodal 4-c unimodal sql topology 2D framework with vertex symbols of {4(4)·6(2)}. In addition, the two identical 2D nets of CP 2 were interpenetrated each other to form a 2D+2D→3D and generate a 2-fold interpenetrating architecture. Moreover, sensing investigations of CP 1 and CP 2 revealed that both of compounds can be used as a highly sensitive and selective multi-responsive luminescent sensor for sensing Cr(2)O(7)(2-), CrO(4)(2-) and antibiotics (TC: Tetracycline; CTC: Chlortetracycline) in H(2)O by exhibiting fluorescence quenching with significant quenching constants (K(sv)=1.369×10(4) M(-1) (Cr(2)O(7)(2-)), 2.003×10(4) M(-1) (CrO(4)(2-)), 5.343×10(4) M(-1) (TC), 8.706×10(4) M(-1) (CTC) for CP 1 and 4.452×10(4) M(-1) (Cr(2)O(7)(2-)), 2.119×10(4) M(-1) (CrO(4)(2-)), 4.175×10(4) M(-1) (TC), 1.257×10(5) M(-1) (CTC) for CP 2). The detection limit are 0.67μM (Cr(2)O(7)(2-)), 0.48μM (Cr(2)O(7)(2-)), 0.23μM (TC), 0.14μM (CTC) for CP 1 and 0.28μM (Cr(2)O(7)(2-)), 0.54μM (CrO(4)(2-)), 0.31μM (TC), 0.098μM (CTC) for CP 2, respectively. In addition, the probable fluorescence quenching mechanism was studied through experiment and theoretical calculation and the co-existance of competitive absorption (CA) and photoinduced electron transfer (PET) progress contributed to such sensing processes.
作者机构：
[Wang, SW; Wang, Shaowei; Liu, Shuang] Chinese Acad Sci, Shanghai Inst Tech Phys, State Key Lab Infrared Phys, 420 Zhongshan Rd, Shanghai 200434, Peoples R China.;[Zhang, Qiuxin] Brandeis Univ, Dept Chem, 415 South St, Waltham, MA 02454 USA.;[Peng, Xingrao; Sun, Yao] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Hu, Cong] Guilin Univ Elect Technol, Guangxi Key Lab Automat Detecting Technol & Instru, Guilin 541004, Peoples R China.
通讯机构：
[Wang, SW ; Sun, Y ; Liu, S] C;Chinese Acad Sci, Shanghai Inst Tech Phys, State Key Lab Infrared Phys, 420 Zhongshan Rd, Shanghai 200434, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
Herein, we show a pair of leucine-rich l- and d-phosphopeptides which self-assemble into twisting nanofibers, whose secondary structures contain a strong beta-sheet component after being dephosphorylated by alkaline phosphatase (ALP). While being incubated with ALP overexpressing osteosarcoma cells, both of the peptides self-assemble in the nuclei and induce cell death. The cell death involves multiple cell death modalities and occurs along with the disruption of cell membranes. Enzyme-instructed self-assembly (EISA) inhibits osteosarcoma cells and shows no side effect to other cells. In addition, the cancer cells hardly gain drug resistance after repeated treatment. This work reports a pair of EISA-based nanofibers to target cell nuclei, and also provides a novel chemotherapeutic agent to inhibit osteosarcoma cells without side effects and drug resistance. Dephosphorylated by the highly expressed alkaline phosphatase, phosphopeptides self-assemble into twisted nanofibers in nuclei to selectively induce the death of osteosarcoma cells.
摘要：
Designing safer chemicals is an integral part of green chemistry that supports good health and well-being. The teaching of molecule design through relevant courses has important implications for the education of sustainable chemists. In these courses, training in toxicology and hazard assessment is essential for students to study benign chemical design that promotes social and environmental justices. However, toxicology training has been rarely included in the course of molecular design, and education of green molecular design at the postgraduate level has been less involved. In this study, we developed an online classroom for toxicology training as a new component of our chemical molecular design course. This class was designed to provide students with a toxicity perspective for viewing chemicals by integrating our three web-based tools. The average score of students' attitude evaluation toward the web-based class was 4.0/5.0, indicating that the toxicology class achieved the expected effects and provided a good experience for students to learn about designing safer chemicals. This work may facilitate the education of green molecular design and inspire students to seriously consider chemically toxic side effects.
作者：
Su, Rina;Wu, Yu;Xu, Weiqing;Tan, Rong;Qin, Ying;...
期刊：
Chemical Engineering Journal,2024年484 ISSN：1385-8947
通讯作者：
Zhu, CZ
作者机构：
[Xu, Weiqing; Qin, Ying; Zhu, Chengzhou; Wu, Yu; Xiao, Runshi; Tan, Rong; Su, Rina; Zhu, CZ; Gu, Wenling] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Xiao, Runshi; Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Sch Mat Sci & Engn, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Wang, Canglong] Chinese Acad Sci, Inst Modern Phys, Lanzhou 730000, Peoples R China.;[Sun, Hongcheng] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.
通讯机构：
[Zhu, CZ ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
Nanozymes have been widely reported to serve as promising alternatives to enzymes. However, insufficient activity is one prominent challenge that limits their further exploitation of applications. To address this issue, photoenzymes, that can borrow solar energy to boost catalysis, inspire the exploration of nanozyme catalysis upon illumination. Herein, a cyano-defective carbon nitride (CCN) nanozyme with photo -enhanced peroxidaselike (POD -like) activity was reported, where the photo -activation enables the 4.15 -fold activity enhancement. Based on in situ characterizations, a self -cascade mechanism was proposed, where CCN can catalyze H2O2 into hydroxyl radical (center dot OH) upon illumination and subsequently capture center dot OH to generate absorbed hydroxyl (*OH) for further catalysis in the dark. Taking advantage of the photo -enhanced activity, a sensing array was successfully constructed for alcohol discrimination. These findings not only set the foundation for photo -enhanced nanozymes but also highlight their potential for practical applications.
关键词：
Cancer biomarkers;Liquid biopsy;Microfluidics;Digital assay;Single molecule detection
摘要：
The current paradigm of cancer management relies on imaging modalities and tissue biopsy to characterize the tumor landscape and devise treatment. As a complementary approach to non-invasive cancer detection, liquid biopsy is gaining interest through the detection of biomarkers circulating in body fluids. However, the wider use of liquid biopsy in the clinical setting is often hindered by limited technologies that can reliably and sensitively detect trace biomarkers in bodily fluids. As one of the most promising emerging technologies, digital single-molecule platforms (DSMPs) offer unparalleled sensitivity using digital read-out that is poised to improve current cancer management. This review provides an overview of the recent development in DSMPs based on digital ELISA, digital flow cytometry, digital surface-enhanced Raman scattering, and other emerging DSMPs for circulating cancer biomarker detection, especially for those that were evaluated on clinical cancer cohorts. DSMPs are well-positioned to address the challenges of studying cancer heterogeneity and trace biomarker discovery with outcomes expected to deliver new tools for cancer screening, treatment monitoring, and tumor recurrence detection.
摘要：
As a hotspot issue of global concern, the abuse of environmental and biological related molecules, including antibiotics, small organic molecules and inorganic anions poses a severe threat to the biological health and ecological environment. Accurate and effective monitoring of these species is of great significance. In this study, one novel nickel(II)-based coordination polymer [Ni(H(2)edda)(2)(Hbmoe)(2)] (Ni-CP) has been successfully designed and synthesized by using the mixed ligands 5,5 '-(ethane-1,2-diylbis(oxy)) diisophthalic acid (H(4)edda) and 1,1 '-bis(1H-benzimidazolyl) oxydiethane (bmoe). Significantly, this framework reveals great thermal and chemical stability and can retain its structural integrity when immersed in water or even in a certain acid/base aqueous solution (pH = 2-13) for a period of time. As expected, this material also exhibits strong fluorescence. Further investigations indicate that as-synthesized Ni-CP can be served as a multi-responsive sensing platform for the highly selective and sensitive detection of nitrofurazone (NFZ), acetylacetone (ACAC), MnO4- and Cr(VI) in aqueous media. The mechanisms for fluorescence quenching have been disclosed through thorough experimental and computational investigations.
摘要：
The role of AXL in various oncogenic processes has made it an attractive target for cancer therapy. Currently, kinase selectivity profiles, especially circumventing MET inhibition, remain a scientific issue of great interest in the discovery of selective type II AXL inhibitors. Starting from a dual MET/AXL-targeted lead structure from our previous work, we optimized a 1,6-naphthyridinone series using molecular modeling-assisted compound design to improve AXL potency and selectivity over MET, resulting in the potent and selective type II AXL-targeted compound 25c. This showed excellent AXL inhibitory activity (IC(50)=1.1nM) and 343-fold selectivity over the highly homologous kinase MET in biochemical assays. Moreover, compound 25c significantly inhibited AXL-driven cell proliferation, dose-dependently suppressed 4T1 cell migration and invasion, and induced apoptosis. Compound 25c also showed noticeable antitumor efficacy in a BaF3/TEL-AXL xenograft model at well-tolerated doses. Overall, this study presented a potent and selective type II AXL-targeted lead compound for further drug discovery.
作者机构：
[Shu, C; Deng, Zhengxi; Xuan, Chenglong; Zhu, Zhiming; Shu, Chao] Cent China Normal Univ CCNU, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, CCNU uOttawa Joint Res Ctr,Natl Key Lab Green Pest, Wuhan 430070, Hubei, Peoples R China.;[Shu, C; Deng, Zhengxi; Xuan, Chenglong; Zhu, Zhiming; Shu, Chao] Anhui Normal Univ, Key Lab Funct Mol Solids, Minist Educ, Wuhu 241000, Anhui, Peoples R China.
通讯机构：
[Shu, C ] C;Cent China Normal Univ CCNU, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, CCNU uOttawa Joint Res Ctr,Natl Key Lab Green Pest, Wuhan 430070, Hubei, Peoples R China.;Anhui Normal Univ, Key Lab Funct Mol Solids, Minist Educ, Wuhu 241000, Anhui, Peoples R China.
摘要：
A thermoinduced radical homolytic substitution cyclization of alkenyl tethered sulfinate esters was displayed under mild metal-free conditions, enabling the functionalization of alkenes and leading to structurally diverse value-added sultine products. The process utilizes readily available substrates using inexpensive 5% benzoyl peroxide (BPO) as an initiator to generate functionalized sultines with broad functional group tolerance in medium to excellent yields in a highly atom-economical manner. In addition, the obtained sultines could be further readily functionalized toward valuable sultone frameworks in one pot. A thermo-catalytic radical chain process was proposed based on mechanistic studies.
摘要：
Herein, a novel fluorescent coordination polymer [Cu2(edda)(bpy)2]Greek ano teleia6H2O (Cu-CP; H4edda = 5,5 '-(ethane-1,2-diylbis(oxy)) diisophthalic acid; bpy = 2,2 '-bipyridine) was designed and successfully architected using semi-rigid tetracarboxylic acid ligand H4edda combined with N,N '-donor linker bpy through a hydrothermal method. Single-crystal structural analysis reveals that the adjacent Cu1 centers are linked by 3 '- and 5-carboxyl groups of edda4-linker to form a one-dimensional Cu(II)-edda4-chain, which is further strutted by 3-and 5 '- carboxyl groups in edda4-ligand to generate a two-dimensional (2D) network with sql topology. Notably, bpy molecules do not actually dedicate to the formation of this 2D network, which merely saturate the configuration of Cu ions. Apart from the great thermal and acid/base stabilities, the pi-conjugated nature of H4edda endows Cu-CP with the traits of strong fluorescent emission in both solid state and aqueous solution. Interestingly, Cu-CP can act as a multifunctional platform for effectively detecting nitrofurazone (NFZ), nitrofurantoin (NFT), Cr2O72-, CrO42-and MnO4- via fluorescence quenching effects in an aqueous system. The fabricated Cu-CP fluorescent sensor shows distinguished sensitivity and anti-interference performance as well as low detection limits (3.55 nM for NFZ; 1.02 nM for NFT; 0.58 mu M for Cr2O72-, 0.68 mu M for CrO42-and 4.59 mu M for MnO4 -). The underlying quenching mechanisms have been studied through in-depth experimental and computational researches.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年89(4):2505-2515 ISSN：0022-3263
通讯作者：
Wu, AX
作者机构：
[Wang, Can; Zhao, Peng] Taizhou Univ, Sch Pharmaceut Sci, Inst Adv Studies, Taizhou 318000, Zhejiang, Peoples R China.;[Wu, An-Xin; Zhou, You; Zhao, Peng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
A novel iodine-promoted difunctionalization of alpha-C sites in enaminones was demonstrated as a means of synthesizing a variety of fully substituted thiazoles by constructing C-C(CO), C-S, and C-N bonds. This transformation allows the realization of enaminones as unusual aryl C2 synthons and simultaneously allows the thioylation and dicarbonylation of alpha-C sites. A preliminary mechanistic study was performed and indicated that the cleavage of C=C bonds in enaminones involves a bicyclization/ring-opening and oxidative coupling sequence.
作者机构：
[Wang, Huai-Yu; Wu, Yan-Dong; Wu, An-Xin; Wu, Chun-Yan; Yu, Zhi-Cheng; Chen, Xiang-Long; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Tang, Bo-Cheng] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, State Key Lab Chem Biol & Drug Discovery, Kowloon, Hong Kong, Peoples R China.;[Li, Anling] Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;[Li, Anling] Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
通讯机构：
[Li, AL ] W;[Wu, YD; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
关键词：
Defluoroarylation;Transition metal free;gem-Difluoroalkenes;Rongalite;Single electron transfer;C-C coupling;Redox reactions;Cross-coupling
摘要：
A transition‐metal‐free allylic defluorination reductive cross‐coupling between CF3‐alkenes and diaryliodonium salts mediated by rongalite has been described for the first time. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates. The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs. Comprehensive Summary The conversion of CF3‐alkenes to gem‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem‐difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs.
