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An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Debugging data-intensive distributed applications running in datacenters is complex and time-consuming because developers do not have practical ways of deterministically replaying failed executions. The reason why building such tools is hard is that non-determinism that may be tolerable on a single node is exacerbated in large clusters of interacting nodes, and datacenter applications produce terabytes of intermediate data exchanged by nodes, thus making full input recording infeasible. We present ADDA, a replay-debugging system for datacenters that has lower recording and storage overhead than existing systems. ADDA is based on two techniques: First, ADDA provides control plane determinism, leveraging our observation that many typical datacenter applications consist of a separate "control plane" and "data plane", and most bugs reside in the former. Second, ADDA does not record "data plane" inputs, instead it synthesizes them during replay, starting from the application's external inputs, which are typically persisted in append-only storage for reasons unrelated to debugging. We evaluate ADDA and show that it deterministically replays real-world failures in Hypertable and Memcached.
Silicon Siting The synthesis of many pharmaceutical and agrochemical compounds requires selective functionalization of multiple different sites on aromatic ring frameworks. The size and electronic properties of the first substituent added can influence where the next one is likely to end up. Cheng and Hartwig (p. 853 , see the Perspective by Tobisu and Chatani ) discovered a rhodium-catalyzed reaction that is particularly sensitive to size that places a silicon substituent as far away as possible from the largest group already on the ring. The silicon group can then be replaced with carbon, oxygen, nitrogen, or halide substituents as needed.
Many active pharmaceuticals, herbicides, conducting polymers, and components of organic light-emitting diodes contain arylamines. For many years, this class of compound was prepared via classical methods, such as nitration, reduction and reductive alkylation, copper-mediated chemistry at high temperatures, addition to benzyne intermediates, or direct nucleophilic substitution on particularly electron-poor aromatic or heteroaromatic halides. However, during the past decade, palladium-catalyzed coupling reactions of amines with aryl halides have largely supplanted these earlier methods. Successive generations of catalysts have gradually improved the scope and efficiency of the palladium-catalyzed reaction. This Account describes the conceptual basis and utility of our latest, "fourth-generation" palladium catalyst for the coupling of amines and related reagents with aryl halides. In the past five years, we have developed these catalysts using the lessons learned from previous generations of catalysts developed in our group and in other laboratories. The ligands on the fourth-generation catalyst combine the chelating properties of the aromatic bisphosphines of the second-generation systems with the steric properties and strong electron donation of the hindered alkylphosphines of the third-generation systems. The currently most reactive catalyst in this class is generated from palladium and a sterically hindered version of the Josiphos family of ligands that possesses a ferrocenyl-1-ethyl backbone, a hindered di-tert-butylphosphino group, and a hindered dicyclohexylphosphino group. This system catalyzes the coupling of aryl chlorides, bromides, and iodides with primary amines, N-H imines, and hydrazones in high yield. The reaction has broad scope, high functional group tolerance, and nearly perfect selectivity for monoarylation. It also requires the lowest levels of palladium that have been used for C-N coupling. In addition, this latest catalyst has dramatically improved the coupling of thiols with haloarenes to form C-S bonds. Using ligands that lacked one or more of the structural elements of the most active catalyst, we examined the effects of individual structural elements of the Josiphos ligand on catalyst activity. This set of studies showed that each one of these elements contributes to the high reactivity and selectivity of the catalyst containing the hindered, bidentate Josiphos ligand. Finally, we examined the effect of electronic properties on the rates of reductive elimination to distinguish between the effect of the properties of the M-N sigma-bond and the nitrogen electron pair. We have found that the effects of electronic properties on C-C and C-N bond-forming reductive elimination are similar. Because the amido ligands contain an electron pair, while the alkyl ligands do not, we have concluded that the major electronic effect is transmitted through the sigma-bond.
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An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
The gold-catalyzed [3+3]-cycloaddition reaction of propargyl esters and azomethine imines has been developed. The reaction provides a rapid entry into a wide range of substituted tetrahydropyridazine derivatives from simple starting materials. A stepwise mechanism involving addition of the 1,3-dipole to a gold-carbenoid intermediate is proposed.
Summary The Rayleigh damping model, which is pervasive in nonlinear response history analysis (RHA) of buildings, is shown to develop ‘spurious’ damping forces and lead to inaccurate response results. We prove that a viscous damping matrix constructed by superposition of modal damping matrices—irrespective of the number of modes included or values assigned to modal damping ratios—completely eliminates the ‘spurious’ damping forces. This is the damping model recommended for nonlinear RHA. Replacing the stiffness‐proportional part of Rayleigh damping by the tangent stiffness matrix is shown to improve response results. However, this model is not recommended because it lacks a physical basis and has conceptual implications that are troubling: hysteresis in damping force–velocity relationship and negative damping at large displacements. Furthermore, the model conflicts with the constant‐damping model that has been the basis for fundamental concepts and accumulated experience about the inelastic response of structures. With a distributed plasticity model, the structural response is not sensitive to the damping model; even the Rayleigh damping model leads to acceptable results. This perspective on damping provides yet another reason to employ the superior distributed plasticity models in nonlinear RHA. OpenSees software has been extended to include a damping matrix defined as the superposition of modal damping matrices. Although this model leads to a full populated damping matrix, the additional computational demands are demonstrated to be minimal. Copyright © 2015 John Wiley & Sons, Ltd.
