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11.
Remote Construction of Chiral Vicinal Tertiary and Quaternary Centers by Catalytic Asymmetric 1,6‐Conjugate Addition of Prochiral Carbon Nucleophiles to Cyclic Dienones 下载免费PDF全文
Yuan Wei Zunwu Liu Xinxin Wu Jie Fei Xiaodong Gu Xiaoqian Yuan Prof. Dr. Jinxing Ye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):18921-18924
An unprecedented remote construction of chiral vicinal tertiary and quaternary centers by a catalytic asymmetric 1,6‐conjugate addition of prochiral carbon nucleophiles to cyclic dienones has been developed. Both 5H‐oxazol‐4‐ones and 2‐oxindoles were found to be very efficient carbon nucleophiles in this reaction at a remote position, giving products with excellent enantio‐ and diastereoselectivities (up to 99 % ee and >19:1 d.r. for 5H‐oxazol‐4‐ones and up to 97 % ee and >19:1 d.r. for 2‐oxindoles). 相似文献
12.
Metal‐Catalyzed β‐Functionalization of Michael Acceptors through Reductive Radical Addition Reactions 下载免费PDF全文
Dr. Jan Streuff Prof. Dr. Andreas Gansäuer 《Angewandte Chemie (International ed. in English)》2015,54(48):14232-14242
Transition‐metal‐catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β‐unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today′s developments. 相似文献
13.
Enantioselective Synthesis of Quaternary Carbon Stereocenters: Addition of 3‐Substituted Oxindoles to Vinyl Sulfone Catalyzed by Pentanidiums 下载免费PDF全文
Dr. Lili Zong Shubo Du Kek Foo Chin Dr. Chao Wang Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2015,54(32):9390-9393
A pentanidium‐catalyzed highly enantioselective conjugate addition of 3‐alkyloxindoles to phenyl vinyl sulfone has been demonstrated. This approach allows the construction of 3,3‐dialkyl‐substituted oxindole frameworks with high yield and excellent enantioselectivity (up to 99 %) under simple phase‐transfer conditions. A variety of oxindoles bearing all‐carbon quaternary stereogenic centers were obtained in the presence of 0.25 mol % pentanidium. Meanwhile, practicality was illustrated by a gram‐scale asymmetric synthesis of two 3,3‐dialkyl‐substituted oxindoles. The resulting adduct can be smoothly transformed to the natural product analogue in a short synthetic route. 相似文献
14.
Sivaiah Areti Jayshree K. Khedkar Sateesh Bandaru Rohit Teotia Jayesh Bellare Chebrolu Pulla Rao 《Analytica chimica acta》2015
A coumarine–imino–C2-glucosyl conjugate (L) was synthesized and characterized. The conjugate L is found to recognize Cu2+ in aqueous HEPES buffer by exhibiting a 95% fluorescence quenching in pH range 7–10 even in the presence of several biologically and ecologically relevant metal ions. Fluorescence on–off behavior has been clearly demonstrated on the basis of the binding variability of Cu2+ to L. The binding has been elicited through the changes observed in fluorescence, absorption, ESI-MS and 1H NMR titrations. All the other thirteen metal ions studied did not show any change in the fluorescence emission. These ions do not interfere with the recognition of Cu2+ by L. The structural features of [CuL]2 complex in both the isomeric forms were established by DFT computational calculations. The utility of L has been demonstrated by showing its sensitivity toward Cu2+ on a thin layer of silica gel. The L gives sensitive fluorescence signals for Cu2+ even in blood serum and exhibits appropriate fluorescence responses in living cells. 相似文献
15.
Lukáš Grajciar 《Journal of computational chemistry》2015,36(20):1521-1535
A new low‐memory modification of the density fitting approximation based on a combination of a continuous fast multipole method (CFMM) and a preconditioned conjugate gradient solver is presented. Iterative conjugate gradient solver uses preconditioners formed from blocks of the Coulomb metric matrix that decrease the number of iterations needed for convergence by up to one order of magnitude. The matrix‐vector products needed within the iterative algorithm are calculated using CFMM, which evaluates them with the linear scaling memory requirements only. Compared with the standard density fitting implementation, up to 15‐fold reduction of the memory requirements is achieved for the most efficient preconditioner at a cost of only 25% increase in computational time. The potential of the method is demonstrated by performing density functional theory calculations for zeolite fragment with 2592 atoms and 121,248 auxiliary basis functions on a single 12‐core CPU workstation. © 2015 Wiley Periodicals, Inc. 相似文献
16.
Dennis Oprych Prof. Dr. Bernd Strehmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4297-4301
NIR and UV exposure of systems comprising upconversion nanoparticles ( UCNP ) based on NaYF4:Tm/Yb@NaYF4, a sensitizer absorbing either in the blue or UV region, and an onium salt with weak coordinating anion resulted in formation of conjugate acid (con-H+). That was namely Ivocerin (di(4-methoxybenzoyl)diethylgermane), ITX (2-iso-propyl thioxanthone), anthracene, pyrene, rubrene, camphore quinone, and a strong fluorescent coumarin (1,1,6,6,8-pentamethyl-2,3,5,6-tetrahyhdro-1H,4H-11-oxa-3a-aza-benzo[de]anthracene-10-one). Quantification occurred by treatment with Rhodamine B lactone whose color switched to intensive red after photolytic formation of con-H+. Exposure with a NIR laser at 980 nm resulted in less con-H+ compared to 395 nm where all sensitizers absorb radiation. UCNP did not mainly interfered formation of con-H+. The different rates obtained in both experiments responsibly explain the failure and success to initiate polymerization of epoxides applying ether 980 nm or 395 nm excitation, respectively. 相似文献
17.
In this article, we study the problem of maximizing expected utility from the terminal wealth with proportional transaction costs and random endowment. In the context of the existence of consistent price systems, we consider the duality between the primal utility maximization problem and the dual one, which is set up on the domain of finitely additive measures. In particular, we prove duality results for utility functions supporting possibly negative values. Moreover, we construct a shadow market by the dual optimal process and consider the utility-based pricing for random endowment. 相似文献
18.
Tadeusz ANTCZAK 《数学物理学报(B辑英文版)》2017,37(4):1133-1150
In this paper, both Fritz John and Karush-Kuhn-Tucker necessary optimality conditions are established for a (weakly) LU-efficient solution in the considered nonsmooth multiobjective programming problem with the multiple interval-objective function. Further, the sufficient optimality conditions for a (weakly) LU-efficient solution and several duality results in Mond-Weir sense are proved under assumptions that the functions constituting the considered nondifferentiable multiobjective programming problem with the multiple interval-objective function are convex. 相似文献
19.
We introduce first a sort of gray-scale morphological dilations and erosions, which might have some further applications in image analysis. Then we show that the dilation and the erosion defined here form adjunctive pairs. The duality between the dilation and the erosion and some other properties, such as the commuting property with translation and homothety, of these operators are discussed as well. 相似文献
20.
Coumarin-based urea and urea–amide scaffolds 1–3 have been designed and synthesized for the selective and naked eye detection of cyanide ion. Of the three, compound 3 exhibits ratiometric fluorescence change selectively in the presence of CN? and validates the rationality in designing anion receptor. Upon interaction with CN?, the color of the solution of 3 in CH3CN under UV exposure becomes bright yellow, which is beneficial for its naked eye detection. Addition of CN? of ~10?4 M brings nice color change from colourless to yellow in ordinary light. The sensing event is supposed to be due to nucleophilic addition of CN? to the coumarin unit enabling intramolecular charge transfer (ICT) mechanism. 相似文献