Circumambulatory rearrangement with characteristics of a 2:1 covalent molecular bevel gear

anti-W(CO)(5)-complexed 9-methyl-9-phosphabicyclo[6.1.0]nonatriene represents a covalently interlocked molecular bevel gear. Correlated movement of the phosphorus atom and the eight-membered ring by way of a "walk" rearrangement makes gear slippage impossible. The gearing motion is transferred to the four-toothed W(CO)(5) propeller connected to the rotating phosphorus atom, enabling a gearing ratio of 2:1 according to B3LYP and Car-Parrinello Molecular Dynamics calculations. Methyl substitution of the eight-membered ring tempers the gearing process, with the PMeW(CO)(5) entity passing the substituted carbon atom only at temperatures above 50 degrees C.     

Efficient library synthesis of imidazoles using a multicomponent reaction and microwave irradiation

Optimization of Radziszewski's four-component reaction employing a microwave-assisted protocol, led to a small library of 48 imidazoles with a success rate of 65% (conversion > 45%). All three diversity points of the four-component reaction were varied. Aromatic and aliphatic inputs were successfully implemented and mono-, di-, tri- and tetrasubstituted imidazoles with various substitution patterns were synthesized. Furthermore, unsymmetrical diketones could successfully be used which improved the intrinsic diversity of the method significantly. If the unsymmetrical diketone 1,2-phenylpropanedione (R¹ and R²) was used two regioisomers were formed. Depending on the type of amine (R⁴) and aldehyde (R³) applied, regioselectivity was modest to good. Based on these results, a reaction mechanism is proposed.     

Diastereoselective multicomponent synthesis of dihydropyridones with an isocyanide functionality

[Structure: see text] In a search for new multicomponent strategies leading to valuable small heterocycles, a new highly diastereoselective four-component reaction (4CR) was found in which a phosphonate, nitriles, aldehydes, and isocyanoacetates combine to afford functionalized 3-isocyano-3,4-dihydro-2-pyridones. In this strategy, initially a 1-azadiene is generated, which is trapped in the same pot by an isocyanoacetate as the fourth component. Multicomponent reactions (MCRs) that lead to heterocycles containing isocyano substituents are unprecedented and offer many possibilities for further differentiation.     

Constrained Quantum Processes

The notion of a continuously observed quantum process constrained at both its initial and final states is introduced. It is shown that under suitable regularity conditions, such a process fulfills a 'least action' principle, wherein action is identified with change of state transitions.     

Synthesis of 4-aminoquinazolines by palladium-catalyzed intramolecular imidoylation of N-(2-bromoaryl)amidines

Compared with the widespread use of carbonylative Pd-catalyzed cross-coupling reactions, similar reactions involving isocyanide insertion are almost virgin territory. We investigated the intramolecular imidoylative cross-coupling of N-(2-bromoaryl)amidines, leading to 4-aminoquinazolines. After thorough optimization of the reaction with respect to palladium source and loading, ligand, base, temperature, and solvent, a small library of 4-aminoquinazolines was prepared to determine the scope of this method. Various substituents are tolerated on the amidine and the isocyanide, providing efficient access to a broad range of diversely substituted 4-aminoquinazolines of significant pharmaceutical interest.     

The time evolution of compound elastic scattering measured by crystal blocking

Using the crystal blocking technique, we have measured the emission distributions of protons near the 〈110〉 axis elastically scattered from a 7000 Å thick single nickel crystal, at 5.65 and 6.50 MeV. These distributions are fitted by an analytic multiple string calculation of the blocking process which yields the time-dependent compound-nucleus decay probability curve. Shape- and compound-elastic cross sections are simultaneously determined in a reaction-model-independent way, as is the mean compound nucleus lifetime. The resulting decay curves for the delayed component are consistent with a single exponential at both energies and show no indication of the presence of level-level correlations. Use of such data in testing recent statistical theories is discussed.     

Multilayer neural networks with extensively many hidden units

The information processing abilities of a multilayer neural network with a number of hidden units scaling as the input dimension are studied using statistical mechanics methods. The mapping from the input layer to the hidden units is performed by general symmetric Boolean functions, whereas the hidden layer is connected to the output by either discrete or continuous couplings. Introducing an overlap in the space of Boolean functions as order parameter, the storage capacity is found to scale with the logarithm of the number of implementable Boolean functions. The generalization behavior is smooth for continuous couplings and shows a discontinuous transition to perfect generalization for discrete ones.