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1.
A Mixed‐Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of Piperarborenine B 下载免费PDF全文
Robert A. Panish Srinivasa R. Chintala Prof. Joseph M. Fox 《Angewandte Chemie (International ed. in English)》2016,55(16):4983-4987
A novel, mixed‐ligand chiral rhodium(II) catalyst, Rh2(S‐NTTL)3(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh2(S‐NTTL)3(dCPA) reveals a “chiral crown” conformation with a bulky dicyclohexylphenyl acetate ligand and three N‐naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium‐catalyzed bicyclobutanation/ copper‐catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8 % overall yield and 92 % ee. 相似文献
2.
Organic azides have been somewhat popularized due to their pivotal role in the emerging field of “click chemistry”. A simple approach has been used for the synthesis of uniform nano Fe‐MIL‐88B‐NH2, and a generic postsynthetic modification route has been developed for the synthesis of azide‐modified nano Fe‐MIL‐88B‐N3. The approach also has been used to synthesize the azide‐modified IRMOF‐3(‐N3). These new azide‐modified Fe‐MIL‐88B‐N3 nanocrystals hold promising potential for the applications in the fields of “click chemistry”, nanotechnology devices and nano composite membranes. 相似文献
3.
Meghann A. White Ashok Maliakal Nicholas J. Turro Jeff Koberstein 《Macromolecular rapid communications》2008,29(18):1544-1548
We have synthesized a “universal ligand” incorporating a phosphonate surface anchor and a terminal alkyne moiety which binds to TiO2 nanoparticles and exhibits excellent dispersity in organic solvents. The alkyne functionality permits attachment of azide terminated polymer shells using “click” chemistry. Thus TiO2 core nanoparticles have been encapsulated with both polystyrene and poly(t‐butyl acrylate) shells. The TiO2‐poly(t‐butyl acrylate) core shell nanoparticles are amenable to further chemical transformation into TiO2‐poly(acrylic acid) nanoparticles through ester hydrolysis. These TiO2‐polyacrylic acid nanoparticles are dispersible in aqueous solution. The resulting core‐shell nanoparticles have been incorporated as high K dielectric films in capacitor and organic thin film transistor devices and are promising new materials for flexible electronics applications.
4.
Liang‐Yun Wang Jia‐Ling Ko Prof. Chien‐Chen Lai Yi‐Hung Liu Prof. Shie‐Ming Peng Prof. Sheng‐Hsien Chiu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8850-8860
Herein, we report a “threading followed by shrinking” approach for the synthesis of rotaxanes by using an “oxygen‐deficient” macrocycle that contained two arylmethyl sulfone units and the dumbbell‐shaped salt bis(3,5‐dimethylbenzyl)ammonium tetrakis(3,5‐trifluoromethylphenyl)borate as the host and guest components, respectively. The extrusion of SO2 from both of the arylmethyl sulfone units of the macrocyclic component in the corresponding [2]pseudorotaxane resulted in a [2]rotaxane that was sufficiently stable to maintain its molecular integrity in CD3SOCD3 at 393 K for at least 5 h. 相似文献
5.
Mugang Pan Guowei Wang Yannan Zhang Junlian Huang 《Journal of polymer science. Part A, Polymer chemistry》2010,48(24):5856-5864
The graft copolymers composed of “Y”‐shaped polystyrene‐b‐poly(ethylene oxide)2 (PS‐b‐PEO2) as side chains and hyperbranched poly(glycerol) (HPG) as core were synthesized by a combination of “click” chemistry and atom transfer radical polymerization (ATRP) via “graft from” and “graft onto” strategies. Firstly, macroinitiators HPG‐Br were obtained by esterification of hydroxyl groups on HPG with bromoisobutyryl bromide, and then by “graft from” strategy, graft copolymers HPG‐g‐(PS‐Br) were synthesized by ATRP of St and further HPG‐g‐(PS‐N3) were prepared by azidation with NaN3. Then, the precursors (Bz‐PEO)2‐alkyne with a single alkyne group at the junction point and an inert benzyl group at each end was synthesized by sequentially ring‐opening polymerization (ROP) of EO using 3‐[(1‐ethoxyethyl)‐ethoxyethyl]‐1,2‐propanediol (EEPD) and diphenylmethylpotassium (DPMK) as coinitiator, termination of living polymeric species by benzyl bromide, recovery of protected hydroxyl groups by HCl and modification by propargyl bromide. Finally, the “click” chemistry was conducted between HPG‐g‐(PS‐N3) and (Bz‐PEO)2‐alkyne in the presence of N,N,N′,N″,N”‐pentamethyl diethylenetriamine (PMDETA)/CuBr system by “graft onto” strategy, and the graft copolymers were characterized by SEC, 1H NMR and FTIR in details. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
6.
Synthesis, Structures, NMR and EPR Investigations of Binuclear Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenoureato)) Complexes of NiII and CuII The synthesis of binuclear CuII and NiII complexes of the quadridentate ligand N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenourea) and their crystal structures are reported. The complexes crystallize monoclinic, P21/c (Z = 2). In the EPR spectra of the binuclear CuII complex exchange‐coupled CuII‐CuII pairs were observed. In addition the signals of a mononuclear CuII species are observed what will be explained with the assumption of an equilibrium between the binuclear CuII‐complex (CuII‐CuII pairs) and oligomeric complexes with “isolated” CuII ions. Detailed 13C and 77Se NMR investigations on the ligand and the NiII complex allow an exact assignment of all signals of the heteroatoms. 相似文献
7.
Bobby Happ Christian Friebe Andreas Winter Dr. Martin D. Hager Dr. Richard Hoogenboom Dr. Ulrich S. Schubert Prof. Dr. 《化学:亚洲杂志》2009,4(1):154-163
The synthesis of a variety of 2‐(1H‐1,2,3‐triazol‐4‐yl)‐pyridines by click chemistry is demonstrated to provide straightforward access to mono‐functionalized ligands. The ring‐opening polymerization of ε‐caprolactone initiated by such a mono‐functionalized ligand highlights the synthetic potential of this class of bidentate ligands with respect to polymer chemistry or the attachment onto surfaces and nanoparticles. The coordination to RuII ions results in homoleptic and heteroleptic complexes with the resultant photophysical and electrochemical properties strongly dependent on the number of these ligands attached to the RuII core. 相似文献
8.
Derrick A. Roberts Prof. Timothy W. Schmidt Prof. Maxwell J. Crossley Prof. Sébastien Perrier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12759-12770
The convergence of supramolecular chemistry and polymer science offers many powerful approaches for building functional nanostructures with well‐defined dynamic behaviour. Herein we report the efficient “click” synthesis and self‐assembly of AB2‐ and AB4‐type multitopic porphyrin–polymer conjugates (PPCs). PPCs were prepared using the copper(I)‐catalysed azide–alkyne cycloaddition (CuAAC) reaction, and consisted of linear polystyrene, poly(butyl acrylate), or poly(tert‐butyl acrylate) arms attached to a zinc(II) porphyrin core via triazole linkages. We exploit the presence of the triazole groups obtained from CuAAC coupling to direct the self‐assembly of the PPCs into short oligomers (2–6 units in length) via intermolecular porphyrinatozinc–triazole coordination. By altering the length and grafting density of the polymer arms, we demonstrate that the association constant of the porphyrinatozinc–triazole complex can be systematically tuned over two orders of magnitude. Self‐assembly of the PPCs also resulted in a 6 K increase in the glass transition temperature of the bulk material compared to a non‐assembling PPC. The modular synthesis and tunable self‐assembly of the triazole‐linked PPCs thus represents a powerful supramolecular platform for building functional nanostructured materials. 相似文献
9.
Dr. Sharifa Hussein Denis Priester Paul Beet Dr. Jonathon Cottom Sam J. Hart Tim James Dr. Robert J. Thatcher Dr. Adrian C. Whitwood Dr. John M. Slattery 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(9):2262-2271
The chemistry of phosphorus(III) ligands, which are of key importance in coordination chemistry, organometallic chemistry and catalysis, is dominated by relatively electron-rich species. Many of the electron-poor PIII ligands that are readily available have relatively small steric profiles. As such, there is a significant gap in “ligand space” where more sterically bulky, electron-poor PIII ligands are needed. This contribution discusses the coordination chemistry, steric and electronic properties of PIII ligands bearing highly fluorinated alkoxide groups of the general form PRn(ORF)3−n, where R=Ph, RF=C(H)(CF3)2 and C(CF3)3; n=1–3. These ligands are simple to synthesize and a range of experimental and theoretical methods suggest that their steric and electronic properties can be “tuned” by modification of their substituents, making them excellent candidates for large, electron-poor ligands. 相似文献
10.
The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States 下载免费PDF全文
Mu‐Chieh Chang Thomas Dann Dr. David P. Day Dr. Martin Lutz Dr. Gregory G. Wildgoose Dr. Edwin Otten 《Angewandte Chemie (International ed. in English)》2014,53(16):4118-4122
The synthesis of bis(formazanate) zinc complexes is described. These complexes have well‐behaved redox‐chemistry, with the ligands functioning as a reversible electron reservoir. This allows the synthesis of bis(formazanate) zinc compounds in three redox states in which the formazanate ligands are reduced to “metallaverdazyl” radicals. The stability of these ligand‐based radicals is a result of the delocalization of the unpaired electron over four nitrogen atoms in the ligand backbone. The neutral, anionic, and dianionic compounds (L2Zn0/?1/?2) were fully characterized by single‐crystal X‐ray crystallography, spectroscopic methods, and DFT calculations. In these complexes, the structural features of the formazanate ligands are very similar to well‐known β‐diketiminates, but the nitrogen‐rich (NNCNN) backbone of formazanates opens the door to redox‐chemistry that is otherwise not easily accessible. 相似文献
11.
From time to time, ill‐defined concepts leads to never‐ending discussions in the chemical literature. “Is there a quadruple bond in the C2 molecule? What about the boron–boron triple bond? Can we uniquely define concepts like aromaticity or bond order at all?” With this tutorial review I would like to point out that some of the contemporary publications in chemistry are characterized by a confusion of ideas and concepts, and in part ill definitions. And, that exactly those ill‐defined concepts lead to never ending controversies in the literature. Examples of well‐ and ill‐defined concepts in chemistry are discussed. 相似文献
12.
Wen‐Yong Lai Dr. Ruidong Xia Dr. Donal D. C. Bradley Prof. Dr. Wei Huang Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(28):8471-8479
We present herein a novel design and the efficient synthesis towards a “homogeneous” starburst fluorene system based on the novel 2,3,7,8,12,13‐hexaaryltruxene scaffold. Controlled microwave heating provides a facile and powerful approach for each step in the synthesis of these bulky materials with large steric hindrance, suggesting an avenue to access structurally well‐defined complex organic semiconductors (OSCs) rapidly and conveniently with high yield and purity. The resulting materials exhibited good thermal stability and an excellent glassy structure as revealed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) as well as wide‐angle X‐ray diffraction (WAXD) studies. Moreover, compared with their corresponding three‐arm‐substituted counterparts T1 – T4 , the introduction of the ortho substituents around the truxene core in Tr1 – Tr4 results in significant blueshifts (of 7–24 nm) of the absorption maxima λmax and higher energy optical gaps (Eg). Comparative studies with corresponding linear, rod‐shaped oligofluorene counterparts (OFX) have revealed that the longest para‐conjugated segment in the TrX (X=1–4) structures plays the dominant role in determining their electronic properties. UV/Vis data and cyclic voltammetry (CV) investigations have indicated that there is little electronic interaction between the arms, even for the shortest armed oligomer Tr1 . A clear linear relationship of both 1/λmax and Eg with the inverse of (n+1) for these branched systems was found. Our findings highlight a novel molecular design comprising an ortho‐substituted, multiarmed architecture that would allow the introduction of isotropic physical and/or mechanical properties, while at the same time maintaining most of the important electronic properties of the rod‐shaped constituents of a fully conjugated system. 相似文献
13.
Qiong Shen Jian Zhang Shuangshuang Zhang Yigang Hao Wei Zhang Weidong Zhang Gaojian Chen Zhengbiao Zhang Xiulin Zhu 《Journal of polymer science. Part A, Polymer chemistry》2012,50(6):1120-1126
An azido‐containing functional monomer, 11‐azido‐undecanoyl methacrylate, was successfully polymerized via ambient temperature single electron transfer initiation and propagation through the reversible addition–fragmentation chain transfer (SET‐RAFT) method. The polymerization behavior possessed the characteristics of “living”/controlled radical polymerization. The kinetic plot was first order, and the molecular weight of the polymer increased linearly with the monomer conversion while keeping the relatively narrow molecular weight distribution (Mw/Mn ≤ 1.22). The complete retention of azido group of the resulting polymer was confirmed by 1H NMR and FTIR analysis. Retention of chain functionality was confirmed by chain extension with methyl methacrylate to yield a diblock copolymer. Furthermore, the side‐chain functionalized polymer could be prepared by one‐pot/one‐step technique, which is combination of SET‐RAFT and “click chemistry” methods. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
14.
In order to model the asymmetric active site of the type‐3 copper enzyme tyrosinase the “doubly asymmetric” binucleating ligand 1‐[bis‐N,N‐(pyrid‐2‐ylmethyl)aminomethyl]‐3‐[N‐(pyrid‐2‐ylmethyl)‐N‐(2‐pyrid‐2‐ylethyl)aminomethyl]benzene (“unsDMPA”) is synthesized and coordinated to copper(I). The O2‐reactivity of the CuI(unsDMPA) complex and its analog derived from the symmetric counterpiece of unsDMPA, DMPA, is investigated. Oxygenation in methanol leads to dicopper(II) bis(μ‐hydroxo) and bis(μ‐methanolato) complexes; the dicopper(II) bis(μ‐hydroxo) complex of the unsDMPA ligand is chiral. Oxygenation in dichloromethane leads to oxidative N‐dealkylation. This is attributed to a tendency of DMPA and unsDMPA complexes to form dicopper bis(μ‐oxo) intermediates, as evidenced by DFT. The implications of these results with respect to the design of tyrosinase model systems are discussed. 相似文献
15.
Bhaskar R. Aluri Dr. Sebastian Burck Dr. Dietrich Gudat Prof. Dr. Mark Niemeyer Dr. Oldamur Holloczki Laszlo Nyulaszi Prof. Dr. Peter G. Jones Prof. Dr. Joachim Heinicke Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12263-12272
Synthetic and structural aspects of the phosphanylation of 1,3‐benzazaphospholides 1Li , ambident benzofused azaphosphacyclopentadienides, are presented. The unusual properties of phospholyl‐1,3,2‐diazaphospholes inspired us to study the coupling of 1Li with chlorodiazaphospholene 2 , which led to the N‐substituted product 3 . Reaction of 1Li with chlorodiphenyl‐ and chlorodicyclohexylphosphane likewise gave N‐phosphanylbenzazaphospholes 4 and 5 , whereas with the more bulky di‐tert‐butyl‐ and di‐1‐adamantylchlorophosphanes, the diphosphanes 6 and 7 are obtained; in the case of 7 they are isolated as a dimeric LiCl(THF) adduct. Structural information was provided by single‐crystal X‐ray diffraction and solution NMR spectroscopy experiments. 2D exchange spectroscopy confirmed the existence of two rotamers of the aminophosphane 5 at room temperature; variable‐temperature NMR spectroscopy studies of 6 revealed two dynamic processes, low‐temperature inversion at ring phosphorus (ΔH≠=22 kJ mol?1, ΔS≠=2 J K?1 mol?1) and very low‐temperature rotation of the tBu2P group. Quantum chemical studies give evidence that 2‐unsubstituted benzazaphospholides prefer N‐phosphanylation, even with bulky chlorophosphanes, and that substituents at the 2‐position of the heterocycle are crucial for the occurrence of P–N rotamers and for switching to alternative P‐substitution, beyond a threshold steric bulk, by both P‐ and 2‐position substituents. 相似文献
16.
Benjamin Schulze Douglas G. Brown Dr. Kiyoshi C. D. Robson Christian Friebe Dr. Michael Jäger Dr. Eckhard Birckner Prof. Dr. Curtis P. Berlinguette Prof. Dr. Ulrich S. Schubert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14171-14180
A series of heteroleptic bis(tridentate) RuII complexes featuring N^C^N‐cyclometalating ligands is presented. The 1,2,3‐triazole‐containing tridentate ligands are readily functionalized with hydrophobic side chains by means of click chemistry and the corresponding cyclometalated RuII complexes are easily synthesized. The performance of these thiocyanate‐free complexes in a dye‐sensitized solar cell was tested and a power conversion efficiency (PCE) of up to 4.0 % (Jsc=8.1 mA cm?2, Voc=0.66 V, FF=0.70) was achieved, while the black dye ((NBu4)3[Ru(Htctpy)(NCS)3]; Htctpy=2,2′:6′,2′′‐terpyridine‐4′‐carboxylic acid‐4,4′′‐dicarboxylate) showed 5.2 % (Jsc=10.7 mA cm?2, Voc=0.69 V, FF=0.69) under comparable conditions. When co‐adsorbed with chenodeoxycholic acid, the PCE of the best cyclometalated dye could be improved to 4.5 % (Jsc=9.4 mA cm?2, Voc=0.65 V, FF=0.70). The PCEs correlate well with the light‐harvesting capabilities of the dyes, while a comparable incident photon‐to‐current efficiency was achieved with the cyclometalated dye and the black dye. Regeneration appeared to be efficient in the parent dye, despite the high energy of the highest occupied molecular orbital. The device performance was investigated in more detail by electrochemical impedance spectroscopy. Ultimately, a promising RuII sensitizer platform is presented that features a highly functionalizable “click”‐derived cyclometalating ligand. 相似文献
17.
《Angewandte Chemie (International ed. in English)》2017,56(47):15141-15145
The bulky bis(4,6‐t Bu‐benzoxazol‐2‐yl)methane ligand system enabled the synthesis of the water‐containing organometallic potassium complex [(18‐crown‐6)K{(4,6‐t Bu‐OCNC6H2)2CH}⋅H2O] ( 2 ), which is an unprecedented example of a water‐stable reactive organopotassium compound. Furthermore, 2 is a rare example of a bis(benzoxazol‐2‐yl)methanide ligand displaying solely O‐coordination to a metal ion. Compound 2 was fully characterized through its solid‐state structure. Furthermore, its behavior in solution was investigated by NMR titration DOSY experiments. These revealed full protonation of the complex only after seven days and the addition of 114 equivalents of water. 相似文献
18.
Serhii Shyshkanov Tu N. Nguyen Fatmah Mish Ebrahim Kyriakos C. Stylianou Paul J. Dyson 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(16):5425-5429
Frustrated Lewis pairs (FLPs) consist of sterically hindered Lewis acids and Lewis bases, which provide high catalytic activity towards non‐metal‐mediated activation of “inert” small molecules, including CO2 among others. One critical issue of homogeneous FLPs, however, is their instability upon recycling, leading to catalytic deactivation. Herein, we provide a solution to this issue by incorporating a bulky Lewis acid‐functionalized ligand into a water‐tolerant metal‐organic framework (MOF), named SION‐105 , and employing Lewis basic diamine substrates for the in situ formation of FLPs within the MOF. Using CO2 as a C1‐feedstock, this combination allows for the efficient transformation of a variety of diamine substrates into benzimidazoles. SION‐105 can be easily recycled by washing with MeOH and reused multiple times without losing its identity and catalytic activity, highlighting the advantage of the MOF approach in FLP chemistry. 相似文献
19.
Carsten von Hänisch PD Dr. 《无机化学与普通化学杂志》2008,634(1):23-29
The range of molecular silicon phosphorus compounds has been extended by some new species containing oligosilane ((R2Si)n; n ≥ 2) or oligosiloxane ((R2SiO)mSiR2; m ≥ 1) fragments bound to phosphorus atoms. Primary and secondary compounds of these types allow for the synthesis of metal derivatives. Such metalated species usually form oligomers and exhibit a versatile structural chemistry with cyclic, polycyclic, and cage‐like patterns. The main results obtained in the field of oligosilane‐ and oligosiloxane‐bridged phosphines will be presented below and the structures of the metal derivatives will be discussed. Moreover, the synthesis of an inorganic ligand on the basis of siloxane‐bridged phosphines will be presented. This compound opens up a new chapter in host‐guest chemistry. 相似文献
20.
Lars Wesemann 《无机化学与普通化学杂志》2004,630(10):1349-1356
Most of the divalent compounds of tin have a lone pair and hence can act as donors. In tin‐transition metal chemistry neutral molecules as well as anions have been studied as ligands. This research report summarizes recent research on coordination compounds with a closo‐heteroborate cage compound stanna‐closo‐dodecaborate [SnB11H11]2?. The syntheses of the first coordination compounds and studies on the ligand abilities of this tin borate are discussed in this article. 相似文献