Cascade intramolecular N-arylation/intermolecular carboamination reactions for the construction of tricyclic heterocycles

A new method for the stereoselective synthesis of tetrahydropyrroloindoles and hexahydropyrroloquinolines of general structure 8 is described. These products are formed through cascade Pd-catalyzed coupling reactions between aryl chlorides and unsaturated amine substrates 5. A single catalyst effects an intramolecular N-arylation reaction followed by an intermolecular alkene carboamination reaction to generate two rings, three bonds, and one stereocenter with good chemoselectivity, diastereoselectivity, and chemical yield.     

Assessment of the electronic structure of 2,2'-pyridylpyrrolides as ligands

The ligand class 2,2'-pyridylpyrrolide is surveyed, both for its structural features and its electronic structure, when attached to monovalent K, Cu, Ag, Au, and Rh. The influence of pyrrolide ring substituents is studied, as well as the question of push/pull interaction between the pyridyl and pyrrolide halves. The π donor ability of the pyrrolide is found to be less than that of an analogous phenyl. However, in contrast to the phenyl analog, the HOMO is pyrrolide π in character for pyridylpyrrolide complexes of copper and rhodium, while it is conventionally metal localized for planar, d(8) rhodium pyridylphenyl. Monovalent three-coordinate copper complexes show great deviations from Y-shaped toward T-shaped structures, including cases where the pyridyl ligand bonds only weakly.     

Vibrational spectroscopy of N-methyliminodiacetic acid (MIDA)-protected boronate ester: examination of the B-N dative bond

N-methyliminodiacetic acid (MIDA)-protected boronate esters are a new class of reagents that offer great promise in iterative Suzuki-Miyaura cross-coupling reactions. Compared to earlier reagents, MIDA esters are easily handled and are benchtop stable under air indefinitely. The success of this new species is tied to its unique molecular architecture. Compared to the simpler B-N containing molecules ammonia borane and trimethylamine borane, MIDA esters are much larger, and the sp(3) hybridized boron atom is secured by two five membered rings, making this molecular class stable for spectroscopic study. Here, we present infrared, Raman, and surface enhanced Raman (SERS) spectra of methylboronic acid MIDA ester. Comparisons of the spectroscopic results to those from electronic structure calculations suggest that the B-N stretching mode in this molecule lies in the range 560-650 cm(-1), making it among the lowest energy vibrations observed to date that can be primarily attributed to B-N stretching.     

Dispersive phonon imaging of InAs

The phonon-focusing patterns of ballistic phonons in InAs are measured in the frequency range 0.1 to 1 THz, in an effort to test the global validity of lattice dynamics models for this semiconductor. Phonon caustic patterns depend sensitively on the shapes of constant frequency surfaces. Several tunnel-junction detectors with sensitivity onsets in this frequency range are used to measure dispersive shifts in the phonon caustics. The measured caustic positions are compared to those predicted by rigid-ion and bond-charge models. Similar to the case of InSb studied by Hebboul and Wolfe, a 6-parameter bond-charge model (BCM)-with force constants determined by neutron, X-ray, and Raman scattering-reproduces the phonon-imaging data both qualitatively and quantitatively. Comparisons of the focusing patterns with an 11-parameter rigid-ion model (RIM) do not show good agreement. New structures are predicted in the phononfocusing patterns at frequencies above about 1.2 THz — presently outside our experimental range-which are highly sensitive to the theoretical modeling.     

Focusing of dispersive phonons in GaAs

The ballistic propagation of highly dispersive phonons in GaAs in analyzed with both a bond-charge model (BCM) and a shell model, and compared to imaging experiments. When scattering is neglected, both models predict dispersive focusing pattern which depend strongly on the selected group velocities. In contrast, velocity-selected phonon images obtained with a PbBi tunnel-junction detector on a 0.7-mm thick crystal, display well-defined caustic lines whose angular positions do not shift at longer delay times. When isotope scattering is considered in the calculation, however, the shell model reproduces the experimental focusing structures remarkably well.For highly dispersive phonons, the bond-charge and shell models predict markedly different phonon-focusing patterns. In particular, a concentration of heat flux along [100] is predicted by BCM forv=1.7–2.0 THz slow-transverse (ST) phonons., but this effect is absent in the shell model. Both models predict new focusing structures in the fasttransverse (FT) mode at high frequencies. Our calculations which include isotope scattering indicate that to observe these new structures considerable technical advances are required in the phonon-imaging experiments.     

Effects related to Stevenson's rule in mass spectral intensity correlations

According to Stevenson's rule, there is a possibility that the chloromethyl and bromomethyl ions in the spectra of alkylhalides may not be formed from the molecular ion by processes described by electronic ground states alone. Since ion intensities at 75 eV are generally considered to be governed by appearance potentials, the operation of Stevenson's rule should influence correlations of intensity data according to the kinetic approach to mass spectra. Deviations from linearity were obtained in correlations of CH₂Br⁺ intensities, but not in those of CH₂CL⁺. Stevenson's rule is of help in explaining the deviations, but by its nature it is not absolute in predicting their occurrence with certainty. Consequently caution must be exercised in the interpretation of new data, particularly for aliphatic compounds.     

Computational investigation of rules governing selective adsorption intensities

Rules previously derived by Wolfe and Weare governing selective adsorption scattering intensities are investigated computationally via the attractive corrugated wall (ACW) model of Harvie and Weare. These rules, which correlate features of the scattering intensity with the form of the atom surface potential, correctly predict intensity features seen in the ACW calculation.     

The asymptotic distribution of lattice points in hyperbolic space

Suppose x and y are two points in the upper half-plane H⁺, and suppose Γ is a discontinuous group of conformal automorphisms of H⁺ having compact fundamental domain S. Denote by N_T(x, y) the number of points of the form γy (γ?Γ) in the closed disc of hyperbolic radius T centered about x, and set $\text{Q}{}_{\mathrm{T}}\text{(x, y) = N}{}_{\mathrm{T}}\text{(x, y) ?}\text{V(T)}\text{A}\text{,}\text{where}\text{V(T)}$ is the hyperbolic area of the disc, and A is the hyperbolic area of S. The asymptotic behavior of the quantity ?_LxL(Q_T(x,y))² is estimated in terms of small eigenvalues of the Laplacian on functions automorphic under Γ.