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81.
Benzylic Functionalization of Anthrones via the Asymmetric Ring Opening of Oxabicycles Utilizing a Fourth‐Generation Rhodium Catalytic System 下载免费PDF全文
Dr. Charles C. J. Loh Dr. Xiang Fang Brendan Peters Prof. Dr. Mark Lautens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13883-13887
While anthrones exist as privileged scaffolds in bioactive molecules, the enantioselective functionalization of anthrones is surprisingly scarce in the literature, with no asymmetric transition metal catalyzed example to date. Herein, we report the first asymmetric transition metal catalyzed benzylic functionalization of anthrones through the rhodium(I) catalyzed desymmetrization of oxabicycles. As previously developed rhodium(I) systems were found to be unsuitable for this substrate, a new robust fourth‐generation [Rh(cod)OH]2 based catalytic system was developed to address synthetic challenges in this protocol. 相似文献
82.
Ring Expansions of Boroles with Diazo Compounds: Steric Control of C or N Insertion and Aromatic/Nonaromatic Products 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Florian Hupp Dr. Ivo Krummenacher Lisa Mailänder Florian Rauch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17844-17849
Access to novel imine‐substituted 1,2‐azaborinines, as well as highly arylated boracyclohexa‐3,5‐dienes has been developed by ring expansion of boroles with diazoalkanes with varying degrees of steric bulk. The formation of a diazoalkane intermediate is also discussed for the reaction of ortho‐brominated p‐tolyl‐azide with 1,2,3,4,5‐pentaphenylborole. Structural details as well as UV/Vis spectroscopic and cyclic voltammetric data are provided. These boron‐containing heterocycles have the potential to serve as building blocks for boron‐containing materials. 相似文献
83.
Inside Cover: Palladium/Zinc Co‐Catalyzed syn‐Stereoselectively Asymmetric Ring‐Opening Reaction of Oxabenzonorbornadienes with Phenols (Chem. Eur. J. 25/2015) 下载免费PDF全文
84.
Synthesis and magnetic properties of organic multilayer films based on the layer‐by‐layer assembly 下载免费PDF全文
Two polymers containing pyridine rings were prepared by free‐radical polymerization and confirmed by Fourier transform infrared and 1H NMR spectra. The preparation of four multilayer films that were obtained by self‐assembly of the polymer and the transition metal neutralized polyelectrolyte on PE substrate was described. UV–vis spectra and atomic force microscopy images were applied to characterize these films and indicate the uniform assembling process. The driving force for building up the multilayer films was identified by infrared spectroscopy to be the coordination interaction. The magnetic behavior was examined as a function of magnetic field strength at 30 kOe and as a function of temperature (5–300 K). All films display strong soft ferromagnetic properties and higher than those of the bulk materials. The magnetic results show that the layer‐by‐layer self‐assembling approach is beneficial to the ordered alignment of adjacent paramagnetic spins and induces better magnetic phenomena. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
85.
86.
One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes 下载免费PDF全文
Dr. Laurence Burroughs Lee Eccleshare John Ritchie Omkar Kulkarni Prof. Dr. Barry Lygo Prof. Dr. Simon Woodward Dr. William Lewis 《Angewandte Chemie (International ed. in English)》2015,54(36):10648-10651
An intramolecular Cannizzaro‐type hydride transfer to an in situ prepared allene enables the synthesis of ortho‐fused 4‐substituted cycloocta‐2,5‐dien‐1‐ones with unprecedented technical ease for an eight‐ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields. 相似文献
87.
Dr. Hans‐Georg Stammler M. Sc. Sebastian Blomeyer Priv.‐Doz. Dr. Raphael J. F. Berger Prof. Dr. Norbert W. Mitzel 《Angewandte Chemie (International ed. in English)》2015,54(46):13816-13820
The charge density distribution of the trimethylaluminum dimer was determined by high‐angle X‐ray diffraction of a single crystal and quantum‐chemical methods and analyzed using the quantum theory of atoms in molecules. The data can be interpreted as Al2Me6 being predominantly ionically bonded, with clear indications of topological asymmetry for the bridging Al? C bonds owing to delocalized multicenter bonding. This interpretation is supported by the calculated magnetic response currents. The data shed new light on the bonding situation in this basic organometallic molecule, which was previously described by contradicting interpretations of bonding. 相似文献
88.
Isotactic rac‐Lactide Polymerization with Copper Complexes: The Influence of Complex Nuclearity 下载免费PDF全文
Solène Fortun Pargol Daneshmand Prof. Dr. Frank Schaper 《Angewandte Chemie (International ed. in English)》2015,54(46):13669-13672
Diiminopyrrolide copper alkoxide complexes, LCuOR (OR1=N,N‐dimethylamino ethoxide, OR2=2‐pyridyl methoxide), are active for the polymerization of rac‐lactide at ambient temperature in benzene to yield polymers with Mw/Mn=1.0–1.2. X‐ray diffraction studies showed bridged dinuclear complexes in the solid state for both complexes. While LCuOR1 provided only atactic polylactide, LCuOR2 produced partially isotactic polylactide (Pm=0.7). The difference in stereocontrol is attributed to a dinuclear active species for LCuOR2 in contrast to a mononuclear species for LCuOR1. 相似文献
89.
Synthesis of Carbazole Alkaloids by Ring‐Closing Metathesis and Ring Rearrangement–Aromatization 下载免费PDF全文
Joydeb Das Prof. Dr. Jyotirmayee Dash 《Angewandte Chemie (International ed. in English)》2015,54(52):15831-15835
Aprocess for the assembly of carbazole alkaloids has been developed on the basis of ring‐closing metathesis (RCM) and ringrearrangement–aromatization (RRA) as the key steps. This method is based on allyl Grignard addition to isatin derivatives to provide smooth access to 2,2‐diallyl 3‐oxindole derivatives through a 1,2‐allyl shift. The diallyl derivatives were used as RCM precursors to afford a novel class of spirocyclopentene‐3‐oxindole derivatives, which underwent a novel RRA reaction to afford carbazole derivatives. The synthetic sequence to carbazoles was shortened by combining the RCM and RRA steps in an orthogonal tandem catalytic process. The utility of this methodology was further demonstrated by the straightforward synthesis of carbazole alkaloids, including amukonal derivative, girinimbilol, heptaphylline, and bis(2‐hydroxy‐3‐methylcarbazole). 相似文献
90.
机抖激光陀螺通过在抖动驱动信号中注入一定强度的随机噪声来消除动态闭锁误差.为了适应机抖激光陀螺小型化和其控制电路数字化的发展,设计了在以抖动驱动信号采用方波形式的基础上,其随机噪声的注入采取了应用寄存器产生的伪随机噪声-m序列按照对方波占空比进行调制的方式,并建立了抖动机构的数学模型,应用所建立的模型通过Matlab中的Simulink进行了仿真.依照随机噪声注入效率的计算方法,文中采用的方式其噪声注入效率要高于以往采用的应用高斯白噪声对交变正弦波驱动信号进行幅值调制的方式,对此进行了实验验证,证明这种随机噪声注入方式效果良好. 相似文献