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101.
Yingying Wang Yang Zhou Min Lei Jinjun Hou Qinghao Jin Dean Guo Wanying Wu 《Tetrahedron》2019,75(9):1180-1185
A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80?°C and furnishes the desired products in good to excellent yields. 相似文献
102.
Minjing Wu Li Xu Zhiyu Cai Shan Huang Yijun Li Lishan Lei Xiaojing Huang 《Photochemistry and photobiology》2020,96(1):170-177
Antimicrobial photodynamic therapy (aPDT) has been recommended for clinical application. Its antibacterial effect on bacteria remained in dentinal tubule was seldom investigated. Here, we evaluated the antibacterial effects of aPDT on Streptococcus mutans (S. mutans) and Lactobacillus acidophilus (L. acidophilus) in planktonic lifestyle, biofilm and carious dentine. Mono-species biofilms or dentinal caries formed on human dentine slices or slabs. Bacterial suspension, biofilms and dentine caries were treated with 0.1 mg mL−1 toluidine Blue O followed by irradiation with a light emission diode (λ − 635 ± 10 nm; 500 mW; 31.5 J cm−2; 60 s) and 0.12% chlorhexidine (CHX), respectively. Residual bacteria were determined by microbial culture analysis and scanning electron microscopy (SEM). One-way analysis of variance (ANOVA) was performed to detect the significance of the variables. Both treatments significantly reduced the number of L. acidophilus in planktonic state, biofilm and carious dentine (P < 0.05). For S. mutans, CHX was only bactericidal against suspension (P < 0.05), while aPDT was effective on both suspension and biofilm (P < 0.05) while not for dentin caries (P > 0.05). Under the experimental conditions assessed, aPDT could be an alternative disinfection method for superficial layer of caries cavity. Its disinfection on bacteria in dentinal tubule of deep layer was deficient. 相似文献
103.
Long‐Zhang Dong Lei Zhang Jiang Liu Qing Huang Meng Lu Wen‐Xin Ji Ya‐Qian Lan 《Angewandte Chemie (International ed. in English)》2020,59(7):2659-2663
A series of stable heterometallic Fe2M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO2 and H2O into HCOOH and O2 without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO2, and high‐valent Fe uses holes to oxidize H2O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g?1 h?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction. 相似文献
104.
We describe the synergistic utilization of titanocene/photoredox dual catalysis driven by visible light for the radical opening/spirocyclization of easily accessible epoxyalkynes. This environmentally benign process uses the organic donor–acceptor fluorophore 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) as a photocatalyst and Hantzsch ester (HE) as an electron donor instead of stoichiometric metallic reductants. The photocatalytic conditions showed exceptionally high reactivity for the synthesis of privileged and synthetically challenging spirocycles featuring a spiro all-carbon quaternary stereocenter. Cyclic voltammetry (CV) studies suggest that Cp2TiIIICl is the catalytically active species.We describe the synergistic utilization of titanocene/photoredox dual catalysis driven by visible light for radical opening/spirocyclization of easily accessible epoxyalkynes.Over the last few decades, radical-based transformations have been increasingly used in organic synthesis due to their salient features, such as ease of generation, mild reaction conditions, and broad functional group compatibility.1,2 As a mild single-electron-transfer (SET) reagent, titanocene monochloride (Cp2TiIIICl) is considered a formidable tool in contemporary radical chemistry due to its ability to promote various fundamental radical-based transformations.3–7 Cp2TiIIICl was first introduced by Nugent and RajanBabu as a very mild stoichiometric reagent for the reductive opening of epoxides.8–11 Later, the catalytic conditions developed by Gansäuer et al. (Scheme 1a)12 employing stoichiometric amounts of active metals in combination with 2,4,6-collidine·HCl further expanded its applications and led to the discovery of a number of novel transformations.13–16 The key to success was the formation of a stable complex A in reactions while decreasing the concentration of active Cp2TiIIICl.17,18 We were interested in the radical opening/cyclization reaction of epoxides which has attracted considerable attention from the synthetic community and has been used numerous times in the synthesis of natural products.19,20 Nevertheless, this reaction required stoichiometric metallic reductants and proceeded slowly particularly with sterically hindered substrates even with high catalyst loading.21 Therefore, the development of an eco-friendly and efficient catalytic system with an expanded substrate scope is highly desirable.Open in a separate windowScheme 1Cp2TiIIICl mediated radical opening/spirocyclization of epoxides; (a) generation of TiIIIvia a metal reduction approach; (b) dual titanocene/photoredox catalysis; (c) examples of drugs and natural products containing heterospirocycles.In recent years metallaphotoredox catalysis has been a new and rapidly growing research subject.22–29 Photoredox processes can directly modulate the oxidation state of metals by electron transfer (ET).30–33 Given that the generation of TiIII is a SET process, we envisioned that the reduction could be facilitated by a photoredox-controlled process while overcoming the aforementioned limitations. On the other hand, spirocycles bearing a chiral spiro all-carbon quaternary carbon are particularly attractive synthetic targets in pharmaceutical development (Scheme 1c).34–36 Such privileged rigid 3D structures offer the concomitant ability to project functionalities in all three-dimensional orientations and led to enhanced pharmacological activities of molecules. Thus significant attention has been paid to their synthesis.37,38 Against this backdrop, here we describe our efforts on the synthesis of various heterospirocycles with the aid of photoredox catalysis.We chose epoxyalkyne 2a as a model substrate for optimization of reaction conditions. After a systematic variation of different reaction parameters, we were pleased to identify the optimal reaction conditions in which a mixture of Cp2TiCl2 (5.0 mol%), [Ir(dtbbpy)(ppy)2]PF6 (1a, 1.0 mol%, EIII/II1/2 = −1.51 V vs. SCE in MeCN), HE (1.2 equiv.) and 2a (1.0 equiv.) in THF at room temperature under the irradiation of a 10 W 450 nm light emitting diode (LED) lamp for 12 hours afforded the desired product 3a in an excellent yield of 96% (13 : 1 d.r.) upon isolation (entry 1). Using a commercial 23 W compact fluorescent lamp (CFL) instead of the 10 W 450 nm LED did not compromise the overall yield of the reaction (entry 2). Notably, when the loading of Cp2TiCl2 was decreased to as low as only 2.0 mol%, the reaction still led to full conversion and produced 3a in 95% yield (entry 3). Further screening of other photosensitizers revealed that the cheap and readily obtained organic dye 4CzIPN 1b is a competent alternative, which led to full conversion with 94% isolated yield (entry 4). Importantly, the reaction did not proceed in the absence of Cp2TiCl2, HE, the photocatalyst, or visible light (entries 5–8). Various solvents, including DMF, MeOH, DMSO, and MeCN, were screened, and they all resulted in poor conversion. The use of other organic electron donors, such as triethylamine, triethanolamine, and ascorbic acid, afforded the product in poor yield.With satisfactory reaction conditions established, we then explored the scope of the cyclization reaction using 4CzIPN as the photosensitizer. Positively, the cyclization reaction worked well and afforded the desired variably heterospirocyclic products in good to excellent yield (Tables 2 and and3).3). The reaction allows the rapid construction of various 5/5, 5/6, 5/7 and 5/8 spiro-ring fused systems (3a–3k) bearing tetrahydrofuran or pyrrolidine motifs via the 5-exo cyclization pathway. Interesting, the diastereoselectivity of the cyclization reaction is highly correlated with the ring size in the substrates. Heterospirocycles containing a 5/5 spiro-ring fused system (3a–3f) were obtained with surprisingly high diastereoselectivity. In some cases (3b, 3c, and 3e) only a single isomer was obtained. The product 3d with a sterically hindered t-butyloxy carbonyl (Boc) protecting group on the N atom was obtained with reduced diastereoselectivity (5 : 1 d.r.). The diastereoselectivities dropped in 5/6, 5/7 and 5/8 spiro-ring fused systems. Given that enantioenriched epoxides could be easily obtained (e.g. via sharpless asymmetric epoxidation), this strategy provides access to optically active spirocycles featuring an all-carbon quaternary stereocenter with the transfer of stereochemical information from epoxides (3c, 3e and 3f). Bis-heterospirocyclic scaffolds were frequently employed in pharmaceutical chemistry. For example, bis-heterospirocyclic 3d is the core structure of DLK inhibitors39 and XEN402 (ref. 40) (scheme 1c), which are used for treating neurodegeneration and congenital erythromelalgia respectively. Furthermore, 6-exo cyclization was also investigated under the standard conditions and smoothly produced a serious of drug-like 6-(trifluoromethyl)-3-pyridinesulfonyl piperidine derivatives including 6/5, 6/6 and 6/7 spiro-ring fused systems (5a–5k) in generally excellent yields. Moreover, cyclization reactions with epoxy-alkynes afforded products containing exocyclic-alkenes and free alcohols which were suitable for further functionalization. This approach provides access to a broad range of novel spirocyclic piperidine and pyrrolidine spirocycles which could be of interest to synthetic and medicinal chemists.Scope of 5-exo and 6-exo cyclizationa,b,c,d
Open in a separate windowaReaction conditions: 2 and 4 (100 mg, 0.1 M in THF).bIsolated yield.c 3c, 3e and 3f were synthesized from enantiomer pure epoxides.dYields within parentheses are based on catalytic conditions using metal as a reductant: CpTi2Cl2 (5 mol%), Zn (2.0 eq.), coll·HCl (2.5 eq.), THF, 20 hours.Additive effect on Ti-catalyzed cyclizationa,b
Open in a separate windowaIn all cases, 2l was used as the substrate and the yield of 3l was determined with 1H NMR.bValues within parentheses are recovery yields of the additives determined with 1H NMR.To examine the scalability of the reaction, gram-scale synthesis of 3a and 3c was performed under the standard conditions with 23 W CFL irradiation. Pleasingly, 92% (3a) and 89% (3c) isolated yields were obtained respectively without any deterioration. Furthermore, an additive-based investigation41 was performed and the results are summarized (Table 3). From this screening, we found that 11 out of 12 additives have no adverse impact on the yield of the reaction. The additives were recovered after the reaction, including benzoxazole 6a, quinazolinone 6b, collidine 6c, tetrahydroquinoline 6d, benzothiazole 6e, indole 6f, and benzofuran 6h. However, quinoxaline 6l strongly inhibited Ti catalysis and 3l was produced in only 23% yield. Notably, the reaction is compatible with various functional groups including phenols 6g, free alcohols and alkene 6j, iodobenzene 6i, ester 3m, ether 3n, dioxolane 5i, lactone 5k, and alkyne 3e. The generality of the dual Ti/4CzIPN catalysis system was further demonstrated by a highly related hydrogen transfer reaction of epoxides which could exclusively provide anti-Markovnikov alcohols (see the ESI S8†). The low-cost of 4CzIPN, broad compatibility with sensitive functional groups, and simple operation conditions are appealing for laboratory and industrial applications.Importantly, the reactions were re-subjected to metal reduction catalytic conditions for comparison with the photocatalytic conditions and the yields are shown within parentheses (Table 2d). It clearly showed that the yields were generally lower. Particularly, we found that the yields dropped dramatically as the steric encumbrance of the substrates increased. For example, substrates containing dioxolane (2g, 4i) or a 7/8-membered-ring (2j, 2k, 4j) afforded the products (3g, 5i, 3j, 3k, 5j) in less than 10% yield with the recovery of the starting materials. 相似文献
105.
Flower-like shaped Bi12TiO20 (Bismuth Titanate)/g-C3N4 (graphite-like carbon nitride) heterojunction was prepared through hydrothermal and sonification methods for the degradation of organic pollutants by visible-light irradiation. The preparation process, chemical structures, and the mechanism of photocatalytic enhancement of the heterostructures were studied systematically. Under visible-light irradiation, the novel flower-like shaped Bi12TiO20/g-C3N4 heterojunction demonstrates prominent activities for the degradation of rhodamine B and p-nitrophenol, with the introduction of flower-like shaped Bi12TiO20 into g-C3N4 composites greatly increasing the activity of pure g-C3N4. This activity enhancement for the heterojunction could be mainly attributed to its low recombination speed of electron–hole pairs, high adsorption ability of organic pollutants, and better optical absorption ability. Moreover, in the visible-light system of Bi12TiO20/g-C3N4, •OH also contributed to the degradation of pollutants, which may explain the enhanced photocatalytic activity after the introduction of Bi12TiO20, as •OH is inactive in pure g-C3N4. Furthermore, 10 wt.% Bi12TiO20/g-C3N4 showed not only high activity but also good stability for degradation of aqueous organic pollutants, implying potential applications prospect. 相似文献
106.
The Random Batch Method proposed in our previous work(Jin et al.J Comput Phys,2020)is not only a numerical method for interacting particle systems and its mean-field limit,but also can be viewed as a model of the particle system in which particles interact,at discrete time,with randomly selected mini-batch of particles.In this paper,we investigate the mean-field limit of this model as the number of particles N→∞.Unlike the classical mean field limit for interacting particle systems where the law of large numbers plays the role and the chaos is propagated to later times,the mean field limit now does not rely on the law of large numbers and the chaos is imposed at every discrete time.Despite this,we will not only justify this mean-field limit(discrete in time)but will also show that the limit,as the discrete time intervalτ→0,approaches to the solution of a nonlinear Fokker-Planck equation arising as the mean-field limit of the original interacting particle system in the Wasserstein distance. 相似文献
107.
Mingshuai He Heshui Yu Peng Lei Shengjie Huang Juanning Ren Wenjing Fan Lifeng Han Haiyang Yu Yuefei Wang Ming Ren Miaomiao Jiang 《Molecules (Basel, Switzerland)》2021,26(5)
Trimethylamine N-oxide (TMAO), as a gut-derived metabolite, has been found to be associated with enhanced risk for atherosclerosis and cardiovascular disease. We presented a method for targeted profiling of TMAO and betaine in serum and food samples based on a combination of one-step sample pretreatment and proton nuclear magnetic resonance spectroscopy. The key step included a processing of sample preparation using a selective solid-phase extraction column for retention of basic metabolites. Proton signals at δ 3.29 and δ 3.28 were employed to quantify TMAO and betaine, respectively. The developed method was examined with acceptable linear relationship, precision, stability, repeatability, and accuracy. It was successfully applied to detect serum levels of TMAO and betaine in TMAO-fed mice and high-fructose-fed rats and also used to determine the contents of TMAO and betaine in several kinds of food, such as fish, pork, milk, and egg yolk. 相似文献
108.
Yan Binggong Kang Lei Kotobuki Masashi He Linchun Liu Bin Jiang Kaiyong 《Journal of Solid State Electrochemistry》2021,25(2):527-534
Journal of Solid State Electrochemistry - We report effectiveness of dopants selected from group 13, such as B, Ga, and In, on the conductivity of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) that is recognized as... 相似文献
109.
110.
Jin Sen Wang Hui Li Lei Luo Xiao Sun Xianshun Zuo Ming Tian Jie Zhang Xiaodong Xie Yi 《中国科学:化学(英文版)》2021,64(11):1964-1969
Science China Chemistry - Extracting photogenerated species from bulk to surface is an essential process for gaining efficient semiconductor-based photocatalysis. However, compared with charged... 相似文献