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991.
He Wang Guodong Tang Xingwei Li 《Angewandte Chemie (International ed. in English)》2015,54(44):13049-13052
Nitrogenation by direct functionalization of C H bonds represents an important strategy for constructing C N bonds. Rhodium(III)‐catalyzed direct amidation of unactivated C(sp3) H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp3) H bonds are amidated under rhodium catalysis in high efficiency using 3‐substituted 1,4,2‐dioxazol‐5‐ones as the amide source. The protocol broadens the scope of rhodium(III)‐catalyzed C(sp3) H activation chemistry, and is applicable to the late‐stage functionalization of natural products. 相似文献
992.
Dr. Hiroshi Takikawa Dr. Arata Nishii Dr. Hiromu Takiguchi Hirotoshi Yagishita Masato Tanaka Dr. Keiichi Hirano Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Ohmori Prof. Dr. Keisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12540-12544
An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen-sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph3MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes. 相似文献
993.
Xuanyu Li Menglei Zha Yaxi Li Dr. Jen-Shyang Ni Tianliang Min Dr. Tianyi Kang Dr. Guang Yang Dr. Hao Tang Prof. Kai Li Prof. Xingyu Jiang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22083-22087
A robust platform is developed to assemble sub-10 nm organic aggregation-induced emission (AIE) particles using four different AIE luminogens (AIEgens) with emissions from green to the second near-infrared window (NIR-II). They are called AIE quantum dots (QDs) to distinguish from typical AIE dots which are larger than 25 nm. Compared with AIE dots that are larger than 25 nm, AIE QDs allow more efficient cellular uptake and imaging without surface modification of any membrane-penetrating peptides or other targeting molecules. NIR-II AIEgens, which have nearly no background fluorescence from organisms, are used to demonstrate that AIE QDs can achieve high contrast at the tumor as small as 80 mm3 and evade the liver more efficiently than AIE dots. AIE QDs hold a good promise for sensitive and precise diagnosis of the latent solid tumor in clinical medicine with much lower off-targeting to the liver than AIE dots. 相似文献
994.
过渡金属催化的脱氢偶联反应是一类高效的化学键构筑方式,但通常需要当量甚至过量的氧化剂以移除脱氢过程产生的电子及质子,其氧化剂残渣对环境有一定的污染.放氢交叉偶联(CCHE)反应摒弃了传统脱氢反应中当量氧化剂的使用,在温和条件下实现碳-氢或杂-氢键直接交叉偶联且唯一副产物为氢气,不仅避免了因原料或产物对氧化剂敏感而发生的副反应,而且在规模化生产中具有很高的附加值,是一种更加绿色的合成策略.本综述从放氢交叉偶联反应机理、化学键构筑类型以及反应延伸等角度归纳并介绍了近年来放氢交叉偶联反应的研究进展,并对该领域的发展前景进行了展望. 相似文献
995.
Yu N Wang C Zhao F Liu L Zhang WX Xi Z 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(18):5670-5679
Addition cyclization of 1,2,3,4-tetrasubstituted 1,4-dilithio-1,3-dienes (Type I) with four equivalents of various aromatic nitriles in the presence of hexamethylphosphoramide (HMPA) gives exclusively fully substituted pyridines in moderate to good yields. Similarly, trisubstituted pyridines can be prepared by the reaction of 2,3-dialkyl- or diaryl-substituted 1,4-dilithio-1,3-dienes (Type II) with nitriles. However, five- or six-membered-ring fused 2,3-disubstituted 1,4-dilithio-1,3-dienes (Type III) reacted with various aromatic and aliphatic nitriles without alpha-hydrogen atoms to afford tricyclic Delta1-bipyrrolines in high yields. The reaction of six-membered-ring fused 2,3-disubstituted 1,4-dilithio-1,3-diene (Type III) with 2-cyanopyridine afforded the corresponding pyridine, and no tricyclic Delta1-bipyrroline was observed. Seven-membered-ring fused dilithiodienes reacted with PhCN or trimethylacetonitrile to afford the corresponding pyridines in good yield. When 1,2,3,4-tetrasubstituted dilithio reagents (Type I) were treated with Me3SiCN, a tandem silylation/intramolecular substitution process readily occurred to yield siloles, whereas the reaction of 2,3-disubstituted dilithio reagents (Types II and III) with Me3SiCN gave rise to (Z,Z)-dienylsilanes with high stereoselectivity. These results revealed that the formation of tricyclic Delta1-bipyrrolines, pyridines, siloles, and (Z,Z)-dienylsilanes are strongly dependent on the substitution patterns of the dilithio butadienes and the nature of the nitriles employed. 相似文献
996.
Asma Akhtar Tasneem Gul Kazi Hassan Imran Afridi Jameel Ahmed Baig Mohammad Bilal Arain 《应用有机金属化学》2020,34(9):e5784
In the present study an innovative tandem ionic liquid-based dispersive microextraction method using an in-syringe air-assisted vesicle system was developed to determine the ultra-trace levels of lead (PbII) and cadmium (CdII) ions in synthetic sweat extract of branded and nonbranded facial cosmetic products. This method is based on injecting 2-amino-3-sulfhydrylpropanoic acid (l -cysteine) (as an eco-friendly chelating agent), hexafluorophosphate ion [PF6−] (as an ion pair agent) and 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM] [PF6] (as an acceptor phase) into the synthetic sweat extract of facial cosmetic products (branded and nonbranded). The acceleration of the dispersion process was carried out by rapid pressure in the syringe through the back-and-forth movement of plunger. The sediment phase was removed following centrifugation, and then hydrophobic complexes of analyte were back-extracted into HNO3 and finally injected into a flame atomic absorption spectrometer. Several factors were systematically optimized. The validity of the methodology was tested by analyzing spiked known standards of both metals in a real sample. The proposed method was applied to the artificial sweat extracts of face makeup products, indicating how much toxic metals from different cosmetics are directly absorbed into skin. 相似文献
997.
Nikolaos V. Tzouras Marina Saab Wim Janssens Thibault Cauwenbergh Prof. Dr. Kristof Van Hecke Dr. Fady Nahra Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5541-5551
The discovery of sustainable and scalable synthetic protocols leading to gold–aryl compounds bearing N-heterocyclic carbene (NHC) ligands sparked an investigation of their reactivity and potential utility as organometallic synthons. The use of a mild base and green solvents provide access to these compounds, starting from widely available boronic acids and various [Au(NHC)Cl] complexes, with reactions taking place under air, at room temperature and leading to high yields with unprecedented ease. One compound, (N,N′-bis[2,6-(di-isopropyl)phenyl]imidazol-2-ylidene)(4-methoxyphenyl)gold, ([Au(IPr)(4-MeOC6H4)]), was synthesized on a multigram scale and used to gauge the reactivity of this class of compounds towards C−H/N−H bonds and with various acids, revealing simple pathways to gold–based species that possess attractive properties as materials, reagents and/or catalysts. 相似文献
998.
Asymmetric “Acetylenic” [3+2] Cycloaddition of Nitrones Catalyzed by Cationic Chiral PdII Lewis Acid 下载免费PDF全文
Highly enantioselective [3+2] cycloaddition of ynones and nitrones has been developed. Very bulky ligand, DTBM‐SEGPHOS, was used for an effective asymmetric induction over distal reaction centers on the linear ynone dipolarophile and for prevention of PdII catalyst deactivation by coordination of the nitrones. The reaction has wide scope of substrates in both ynones and nitrones. 相似文献
999.
Dr. Guillaume Naulet Aline Delamare Dr. Gilles Guichard Dr. Guillaume Compain 《European journal of organic chemistry》2023,26(10):e202300164
We report the direct incorporation of the hexafluoroisobutyl group on a chiral glycine Schiff base complex mediated by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The fluoroalkylation involves 2-(bromomethyl)-1,1,1,3,3,3-hexafluoropropane reagent, which generates in situ hexafluoroisobutylene (HFIB), and reacts then with the enolate through a tandem allylic shift/hydrofluorination process. We showed that the use of neutral organic base DBU generates in situ an original DBU⋅HF salt, which preserves the fluoride nucleophilicity and acts as a fluorinating agent. This fluoride salt promotes the hydrofluorination of the pentafluorinated alkene overcoming the usual fluoride β-elimination observed with α-CF3-vinyl reagents. With alkali metal bases, by contrast, the hydrofluorination is disfavored and the pentafluorinated alkene intermediate is obtained predominantly. This study highlights the critical role of the fluoride counter ion to preserve its nucleophilicity. The protocol is amenable to multidecagram scale synthesis of enantiopure (S)- and (R)-5,5,5,5’,5’,5’-hexafluoroleucine and their N-Fmoc or N-Boc derivatives in good overall yield. 相似文献
1000.
Chaitanya Ittamalla Saikrishna Chintha Dr. Nagaraju Medishetti Dr. Jagadeesh Babu Nanubolu Dr. Krishnaiah Atmakur 《European journal of organic chemistry》2023,26(22):e202300357
Synthesis of title compounds were accomplished by a reaction of vinyl malononitriles and arylidene pyrazolones catalyzed by base. This protocol proceeds via Michael addition followed by intramolecular cyclization leading to the formation of two new C−C bonds. Further the same reaction was also conducted with α,α-dicyano olefins and vinyl malononitriles to furnish 1,6-dihydro biphenyl compounds. Simple reaction conditions, high yields and compatibility are the advantages of this protocol. 相似文献