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21.
Saeed Bahadorikhalili Sayyad Mohammadi Mehdi Asadi Maliheh Barazandeh Mohammad Mahdavi 《中国化学会会志》2020,67(1):160-164
In this paper, multicomponent reaction of amine, carbon disulfide and fluoronitrobenzene is reported for the synthesis of nitrophenyl methylcarbamodithioate derivatives. The method is based on the nucleophilic attack of the activated methylcarbamodithioate salt to fluoronitrobenzene. Several starting materials are tested and successfully produced the corresponding nitrophenyl methylcarbamodithioate. A possible mechanism for the reaction is suggested. 相似文献
22.
The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine. 相似文献
23.
Ain Uddin Kyle N. Plunkett 《Journal of polymer science. Part A, Polymer chemistry》2020,58(22):3165-3169
A series of donor-acceptor copolymers with dicyclopenta[cd,jk]pyrene and dicyclopenta[cd,lm]perylene acceptor units was prepared via palladium catalyzed cyclopenta-annulation reactions. The acceptor units were paired with diethynyl containing donor groups based on benzo[1,2-b:4,5-b’]dithiophene, thieno[3,2-b]thiophene, and 4-octyl-4H-dithieno[3,2-b:2′,3′-d]pyrrole to create six polymer variants. The cyclopentannulation polymerization resulted in copolymers with molecular weights (Mn) of 6–14 kDa and broad light absorption in the visible region with band gaps of 1.38–1.85 eV. The synthetic methodology, as well as optoelectronic properties, including thin-film absorption and cyclic voltammetry, of the donor-acceptor copolymers are presented. 相似文献
24.
Dr. Jean-Noël Rebilly Wenli Zhang Dr. Christian Herrero Dr. Hachem Dridi Dr. Katell Sénéchal-David Dr. Régis Guillot Prof. Frédéric Banse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):659-668
Rieske dioxygenases are metalloenzymes capable of achieving cis-dihydroxylation of aromatics under mild conditions using O2 and a source of electrons. The intermediate responsible for this reactivity is proposed to be a cis-FeV(O)(OH) moiety. Molecular models allow the generation of a FeIII(OOH) species with H2O2, to yield a FeV(O)(OH) species with tetradentate ligands, or {FeIV(O); OH.} pairs with pentadentate ones. We have designed a new pentadentate ligand, mtL42, bearing a labile triazole, to generate an “in-between” situation. Two iron complexes, [(mtL42)FeCl](PF6) and [(mtL42)Fe(OTf)2]), were obtained and their reactivity towards aromatic substrates was studied in the presence of H2O2. Spectroscopic and kinetic studies reflect that triazole is bound at the FeII state, but decoordinates in the FeIII(OOH). The resulting [(mtL42)FeIII(OOH)(MeCN)]2+ then lies on a bifurcated decay pathway (end-on homolytic vs. side-on heterolytic) depending on the addition of aromatic substrate: in the absence of substrate, it is proposed to follow a side-on pathway leading to a putative (N4)FeV(O)(OH), while in the presence of aromatics it switches to an end-on homolytic pathway yielding a {(N5)FeIV(O); OH.} reactive species, through recoordination of triazole. This switch significantly impacts the reaction regioselectivity. 相似文献
25.
Kapil Mohan Saini Rakesh K. Saunthwal Sushmita Akhilesh K. Verma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1017-1021
Transition-metal-free regioselective synthesis of functionalized amino-indenones by the reaction of ortho-alkynylaldehydes with a broad range of primary amines by intramolecular cyclization has been described. The designed reaction proceeds through KOH-mediated Prins-type cyclization and DMSO-promoted oxidation of the cyclopent-2-en-1-one system. The proposed mechanism and role of solvent were well supported by control experiments. For the first time, we have disclosed the reverse reactivity of (2-alkynyl)-arylaldimines in a super basic system. 相似文献
26.
Lukas Lohmeyer Dr. Elisabeth Kaifer Prof. Hubert Wadepohl Prof. Hans-Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5834-5845
New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps. 相似文献
27.
Dr. Rebecca L. Greenaway Dr. Valentina Santolini Dr. Filip T. Szczypiński Dr. Michael J. Bennison Dr. Marc A. Little Andrew Marsh Dr. Kim E. Jelfs Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3718-3722
Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling. 相似文献
28.
Wei Xu Dr. Karoly Kozma Tianxiang Sha Yi-Jen Wu Prof. May Nyman Prof. Michael M. Lerner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(36):8101-8104
The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but MI dimeric complexes with M−M bonding, [M2(en)2]2+, (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor-type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en)2]2+. Here, the facile interconversion between dimeric-MI and monomeric-MII intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X-ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M2(en)2]2+ or [M(en)2]2+ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M0→M2+ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage. 相似文献
29.
Yukimasa Aida Juntaro Nogami Dr. Haruki Sugiyama Prof. Dr. Hidehiro Uekusa Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12579-12588
The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of >99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter. 相似文献
30.
Weimin Shi Jingjie Zhang Fengqian Zhao Wei Wei Fang Liang Yin Zhang Prof. Dr. Shaolin Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14823-14827
In this work, a mild and transition-metal-free approach for the nucleophilic aromatic substitution (SNAr) of unactivated fluoroarenes with primary aliphatic amines to form aromatic amines is reported. This reaction is facilitated by the formation of cationic fluoroarene radical intermediates in the presence of an acridinium-based organic photocatalyst under blue-light irradiation. Various electron-rich and electron-neutral fluoroarenes are competent electrophiles for this transformation. A wide range of primary aliphatic amines, including amino acid esters, dipeptides, and linear and branched amines are suitable nucleophiles. The synthetic utility of this protocol is demonstrated by the late-stage functionalization of several complex drug molecules. 相似文献