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831.
Nadin A Hattotuwagama C Churcher I 《Angewandte Chemie (International ed. in English)》2012,51(5):1114-1122
The pharmaceutical industry remains solely reliant on synthetic chemistry methodology to prepare compounds for small-molecule drug discovery programmes. The importance of the physicochemical properties of these molecules in determining their success in drug development is now well understood but we present here data suggesting that much synthetic methodology is unintentionally predisposed to producing molecules with poorer drug-like properties. This bias may have ramifications to the early hit- and lead-finding phases of the drug discovery process when larger numbers of compounds from array techniques are prepared. To address this issue we describe for the first time the concept of lead-oriented synthesis and the opportunity for its adoption to increase the range and quality of molecules used to develop new medicines. 相似文献
832.
Peng Xiong Fan Xu Xiang‐Yang Qian Yared Yohannes Dr. Jinshuai Song Prof. Dr. Xin Lu Prof. Dr. Hai‐Chao Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4379-4383
A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond. 相似文献
833.
Jan Bornholdt Dr. Jakob Felding Dr. Rasmus P. Clausen Dr. Jesper L. Kristensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(41):12474-12480
The pyrimidine‐2‐sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl‐protected 2‐methyl‐aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase‐B inhibitor marketed for the treatment of Parkinson’s disease. 相似文献
834.
Cong Tian Leonardo Massignan Tjark H. Meyer Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2018,57(9):2383-2387
Electrochemistry enabled C?H/N?H functionalizations at room temperature by external oxidant‐free cobalt catalysis. Thus, the sustainable cobalt electrocatalysis manifold proceeds with excellent levels of chemoselectivity and positional selectivity, and with ample scope, thus allowing electrochemical C?H activation under exceedingly mild reaction conditions at room temperature in water. 相似文献
835.
In the paper, the behaviour of interior point algorithms is analyzed by using a variable metric method approach. A class of
polynomial variable metric algorithms is given achieving O ((n/β)L) iterations for solving a canonical form linear optimization problem with respect to a wide class of Riemannian metrics,
wheren is the number of dimensions and β a fixed value. It is shown that the vector fields of several interior point algorithms
for linear optimization is the negative Riemannian gradient vector field of a linear a potential or a logarithmic barrier
function for suitable Riemannian metrics.
Research Partially supported by the Hungarian National Research Foundation, Grant Nos. OTKA-T016413 and OTKA-2116. 相似文献
836.
With the aid of selected examples an overview is given of the development trends in highly discriminative reactions using organoaluminum compounds. (1) Isomerization of substituted oxiranes into allyl alcohols has been effected both stereo- and regioselectively by means of a new organoaluminum reagent, diethylaluminum 2,2,6,6-tetramethylpiperidide (DATMP); this reaction which provides a new route for the regiospecific transformation of allyl alcohols into 1,3-dienes. (2) A novel nonenzymic heterolysis of allylic phosphates of terpenoids has been effected by organoaluminum compounds and has enabled development of a new method for the selective synthesis of cyclic terpenes. (3) The reductive condensation of α-haloketones with carbonyl compounds in the presence of diethylaluminum chloride and zinc affords β-hydroxy-carbonyl derivatives in good yields with exclusion of undesired self-condensations products. 相似文献
837.
N. A. Abrosimov 《Mechanics of Composite Materials》1999,35(6):495-506
Nonlinear three-dimensional problems of dynamic deformation, buckling, and posteritical behavior of composite shell structures under pulsed loads are analyzed. The structure is assumed to be made of rigidly joined plates and shells of revolution along the lines coinciding with the coordinate directions of the joined elements. Individual structural elements can be made of both composite and conventional isotropic materials. The kinematic model of deformation of the structural elements is based on Timoshenko-type hypotheses. This approach is oriented to the calculation of nonstationary deformation processes in composite structures under small deformations but large displacements and rotation angles, and is implemented in the context of a simplified version of the geometrically nonlinear theory of shells. The physical relations in the composite structural elements are based on the theory of effective moduli for individual layers or for the package as a whole, whereas in the metallic elements this is done in the framework of the theory of plastic flow. The equations of motion of a composite shell structure are derived based on the principle of virtual displacements with some additional conditions allowing for the joint operation of structural elements. To solve the initial boundary-value problem formulated, an efficient numerical method is developed based on the finite-difference discretization of variational equations of motion in space variables and an explicit second-order time-integration scheme. The permissible time-integration step is determined using Neumann's spectral criterion. The above method is especially efficient in calculating thin-walled shells, as well as in the case of local loads acting on the structural element, when the discretization grid has to be condensed in the zones of rapidly changing solutions in space variables. The results of analyzing the nonstationary deformation processes and critical loads are presented for composite and isotropic cylindrical shells reinforced with a set of discrete ribs in the case of pulsed axial compression and external pressure.Scientific Research Institute of Mechanics, Lobachevskii Nizhegorodsk State University, N. Novgorod, Russia. Translated from Mekhanika Kompozitnykh Materialov, Vol. 35, No. 6, pp. 757–776, November–December, 1999. 相似文献
838.
We present robust and asymptotically optimal iterative methods for solving 2D anisotropic elliptic equations with strongly jumping coefficients, where the direction of anisotropy may change sharply between adjacent subdomains. The idea of a stable preconditioning for the Schur complement matrix is based on the use of an exotic non‐conformal coarse mesh space and on a special clustering of the edge space components according to the anisotropy behavior. Our method extends the well known BPS interface preconditioner [2] to the case of anisotropic equations. The technique proposed also provides robust solvers for isotropic equations in the presence of degenerate geometries, in particular, in domains composed of thin substructures. Numerical experiments confirm efficiency and robustness of the algorithms for the complicated problems with strongly varying diffusion and anisotropy coefficients as well as for the isotropic diffusion equations in the ‘brick and mortar’ structures involving subdomains with high aspect ratios. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
839.
Z.W. Yang M.Z. Liu Juan J. Nieto 《Journal of Computational and Applied Mathematics》2009,233(4):990-1004
In this paper we deal with the numerical solutions of Runge–Kutta methods for first-order periodic boundary value differential equations with piecewise constant arguments. The numerical solution is given by the numerical Green’s function. It is shown that Runge–Kutta methods preserve their original order for first-order periodic boundary value differential equations with piecewise constant arguments. We give the conditions under which the numerical solutions preserve some properties of the analytic solutions, e.g., uniqueness and comparison theorems. Finally, some experiments are given to illustrate our results. 相似文献
840.
本文从热传导离散物理模型上论证了集中质量热容矩阵模型可以在离散点上满足热量守恒定律,采用它就可以避免许多热传导时间积分中的不合理现象。几个算例表明了该模型具有良好的精度。 相似文献