Derivatization of 1-phenyl substituted 4-amino-2-benzazepin-3-ones: evaluation of Pd-catalyzed coupling reactions

Several Pd-catalyzed reactions were explored to further functionalize the bromo-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepin-3-one scaffold (Aba). We report in this paper suitable reaction conditions for Suzuki, Buchwald-Hartwig, and Heck reactions. The substitution pattern of the starting aminobenzazepinone turned out to be crucial for the success of these transition metal-catalyzed reactions, which often required modifications of standard literature procedures. The Pd-catalyzed methods provide access to novel substitution patterns of the Aba scaffold.     

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by ¹H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures.     

Artificial time integration

Many recent algorithmic approaches involve the construction of a differential equation model for computational purposes, typically by introducing an artificial time variable. The actual computational model involves a discretization of the now time-dependent differential system, usually employing forward Euler. The resulting dynamics of such an algorithm is then a discrete dynamics, and it is expected to be “close enough” to the dynamics of the continuous system (which is typically easier to analyze) provided that small – hence many – time steps, or iterations, are taken. Indeed, recent papers in inverse problems and image processing routinely report results requiring thousands of iterations to converge. This makes one wonder if and how the computational modeling process can be improved to better reflect the actual properties sought. In this article we elaborate on several problem instances that illustrate the above observations. Algorithms may often lend themselves to a dual interpretation, in terms of a simply discretized differential equation with artificial time and in terms of a simple optimization algorithm; such a dual interpretation can be advantageous. We show how a broader computational modeling approach may possibly lead to algorithms with improved efficiency. AMS subject classification (2000)  65L05, 65M32, 65N21, 65N22, 65D18     

Packing Non-Zero A-Paths In Group-Labelled Graphs

Let G=(V,E) be an oriented graph whose edges are labelled by the elements of a group Γ and let A⊂V. An A-path is a path whose ends are both in A. The weight of a path P in G is the sum of the group values on forward oriented arcs minus the sum of the backward oriented arcs in P. (If Γ is not abelian, we sum the labels in their order along the path.) We are interested in the maximum number of vertex-disjoint A-paths each of non-zero weight. When A = V this problem is equivalent to the maximum matching problem. The general case also includes Mader's S-paths problem. We prove that for any positive integer k, either there are k vertex-disjoint A-paths each of non-zero weight, or there is a set of at most 2k −2 vertices that meets each of the non-zero A-paths. This result is obtained as a consequence of an exact min-max theorem. These results were obtained at a workshop on Structural Graph Theory at the PIMS Institute in Vancouver, Canada. This research was partially conducted during the period the first author served as a Clay Mathematics Institute Long-Term Prize Fellow.     

Writhing instabilities of twisted rods: from infinite to finite length

We use three different approaches to describe the static spatial configurations of a twisted rod as well as its stability during rigid loading experiments. The first approach considers the rod as infinite in length and predicts an instability causing a jump to self-contact at a certain point of the experiment. Semi-finite corrections, taken into account as a second approach, reveal some possible experiments in which the configuration of a very long rod will be stable through out. Finally, in a third approach, we consider a rod of real finite length and we show that another type of instability may occur, leading to possible hysteresis behavior. As we go from infinite to finite length, we compare the different information given by the three approaches on the possible equilibrium configurations of the rod and their stability. These finite size effects studied here in a 1D elasticity problem could help us guess what are the stability features of other more complicated (2D elastic shells for example) problems for which only the infinite length approach is understood.     

Stark's conjecture over complex cubic number fields

Systematic computation of Stark units over nontotally real base fields is carried out for the first time. Since the information provided by Stark's conjecture is significantly less in this situation than the information provided over totally real base fields, new techniques are required. Precomputing Stark units in relative quadratic extensions (where the conjecture is already known to hold) and coupling this information with the Fincke-Pohst algorithm applied to certain quadratic forms leads to a significant reduction in search time for finding Stark units in larger extensions (where the conjecture is still unproven). Stark's conjecture is verified in each case for these Stark units in larger extensions and explicit generating polynomials for abelian extensions over complex cubic base fields, including Hilbert class fields, are obtained from the minimal polynomials of these new Stark units.

     

Solutions of the WDVV Equations and Integrable Hierarchies of KP Type

We show that reductions of KP hierarchies related to the loop algebra of SL_n with homogeneous gradation give solutions of the Darboux-Egoroff system of PDE's. Using explicit dressing matrices of the Riemann-Hilbert problem generalized to include a set of commuting additional symmetries, we construct solutions of the Witten– Dijkgraaf–E. Verlinde–H. Verlinde equations.