Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids

As a key element in the construction of complex organic scaffolds, the formation of C?C bonds remains a challenge in the field of synthetic organic chemistry. Recent advancements in single‐electron chemistry have enabled new methods for the formation of various C?C bonds. Disclosed herein is the development of a novel single‐electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium in situ followed by a radical–radical coupling was made possible merging N‐heterocyclic carbene (NHC) and photoredox catalysis. The utility of this protocol in synthesis was showcased in the late‐stage functionalization of a variety of pharmaceutical compounds. Preliminary investigations using chiral NHCs demonstrate that enantioselectivity can be achieved, showcasing the advantages of this protocol over alternative methodologies.     

Nuclear resonance vibrational spectra of five-coordinate imidazole-ligated iron(II) porphyrinates

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).     

Sulfoxide as a ligand in iron(II) porphyrinates: S- or O-bound?

In order to study the bonding of sulfoxides to iron(II) porphyrinates, an equilibrium study of Fe(TPP) with tetramethylenesulfoxide (TMSO) has been performed. UV-vis spectra at different concentrations of TMSO have shown distinct character belonging to three species: four-coordinate Fe(II)(TPP), five-coordinate [Fe(II)(TPP)(TMSO)], and six-coordinate [Fe(II)(TPP)(TMSO)2]. The isosbestic points for the low TMSO concentrations suggest that the equilibrium constant K1 is much larger than K2. Analysis of spectral data by the nonlinear least-squares program SQUAD gives K1 = 267 and K2 approximately 1. Even though the five-coordinate species is the dominant species under the synthetic conditions, only the six-coordinate species was crystallized and characterized by an X-ray diffraction study. [Fe(TPP)(TMSO)2] (C52H44Fe-N4O2S2): monoclinic, P2(1)/c, a = 11.2580(3) A, b = 15.9262(5) A, c = 12.3930(4) A, beta = 116.246(1) degrees , V = 1992.95(10) A3, Z = 2. X-ray crystallography demonstrates the complex is a low-spin bis-TMSO ligated species. The average Fe-Np distance is 1.999(4) A. The most important feature is that TMSO is coordinated to iron(II) by the sulfur donors, not oxygen. The Fe-S distance is 2.2220(3) A.     

Signal broadening in potential modulation differentiation

A method is developed for handling the effect of a finite amplitude on the results of potential modulation differentiation. The procedure is applied to harmonic modulation and allows to extrapolate measured Fourier coefficients to zero modulation amplitude. It is therefore possible to use modulation amplitudes as dictated by signal-to-noise considerations avoiding dynamical broadening of the detected signal. The formalism can be easily extended to combine with dynamic background subtraction. Examples are given for soft x-ray appearance potential measurements.     

Unoccupied electronic states on Ni(100) induced by A c(2 × 2) oxygen overlayer

Bremsstrahlung isochromat spectra at hω₀ = 9.7 eV for electrons normally incident on a clean Ni(100) surface are compared to emission from Ni(100) with an ordered c(2 × 2) oxygen overlayer. We observe strong emission due to adsorbate induced antibonding electronic states near E_F and a simultaneous attenuation of previously identified direct bulk interband transitions. The results are in accord with theoretical predictions.     

Grüneisen ratio divergence at the quantum critical point in CeCu(6-x)Agx

The heavy-fermion system CeCu6-xAgx is studied at its antiferromagnetic quantum critical point, xc=0.2, by low-temperature (T> or =50 mK) specific heat, C(T), and volume thermal expansion, beta(T), measurements. Whereas C/T proportional to log((T0/T) would be compatible with the predictions of the itinerant spin-density-wave (SDW) theory for two-dimensional critical spin fluctuations, beta(T)/T and the Grüneisen ratio, Gamma(T) proportional to beta/C, diverge much weaker than expected, in strong contrast to this model. Both C and beta, plotted as a function of the reduced temperature t=T/T0 with T0=4.6 K, are similar to what was observed for YbRh2(Si(0.95)Ge(0.05))2 (T0=23.3 K), indicating a striking discrepancy to the SDW prediction in both systems.     

Synthesis of (-)-epibatidine

The synthesis of (-)-epibatidine has been accomplished utilizing a highly exo-selective asymmetric hetero Diels-Alder reaction. The key steps employed to transform the resulting bicycle into the natural product include a fluoride-promoted fragmentation and a Hofmann rearrangement. Reaction: see text.     

Frequency-stable operation of a diode-pumped continuous-wave RbTiOAsO(4) optical parametric oscillator

Frequency-stable operation of a diode-pumped continuous-wave optical parametric oscillator (OPO) of RbTiOAsO(4) is demonstrated. Piezoelectric and fast electro-optic control of the optical length of the two-mirror OPO cavity (resonant for the pump and the idler waves) compensates for thermal changes in the refractive index of the OPO crystal (induced by absorption of pump light) and acoustic perturbations of the cavity length. Pumped by 405mW of the 810-nm output of a GaAlAs masterf-oscillator-tapered-amplifier diode laser system, the OPO generates a power-stable single-frequency signal wave at 1.24microm with an output of 84mW and a spectral bandwidth of less than 10MHz.     

Reliability optimization of friction-damped systems using nonlinear modes

A novel probabilistic approach for the design of mechanical structures with friction interfaces is proposed. The objective function is defined as the probability that a specified performance measure of the forced vibration response is achieved subject to parameter uncertainties. The practicability of the approach regarding the extensive amount of required design evaluations is strictly related to the computational efficiency of the nonlinear dynamic analysis. Therefore, it is proposed to employ a recently developed parametric reduced order model (ROM) based on nonlinear modes of vibration, which can facilitate a decrease of the computational burden by several orders of magnitude.