A concise synthesis of both enantiomers of ligand 2 and rhodium complex 5 is presented. The crux of the synthesis is a chiral HPLC separation of the enantiomers of 4. Rhodium complex 5 possesses three hindered quadrants in the steric environment within which a substrate binds. Evidence is presented that this configuration leads to high enantioselectivity (>99% ee) for rhodium-catalyzed asymmetric hydrogenation of alpha-acetamido dehydroamino acids, 6a-e. High enantioselectivities are also reported for the hydrogenation of a substrate precursor, 8, of pharmaceutical candidate, pregabalin. Advantages for large-scale hydrogenation of 8 using catalyst 5a vs Rh-Me-DuPhos are discussed.

A long-sought empty non-IPR fullerene, (#11188)C72, which is more stable than the sole IPR isomer in the fullerene[72] family, has been retrieved and crystallographically characterized as (#11188)C72Cl4. Mass spectrometric data support the facile dechlorination of (#11188)C72Cl4 and, in turn, the possible stability of pristine (#11188)C72.

This paper reports verification and validation of linear simulations of Alfvén eigenmodes in the current ramp phase of DIII-D L-mode discharge #159243 using gyrokinetic, gyrokinetic-MHD hybrid, and eigenvalue codes. Using a classical fast ion profile, all simulation codes find that reversed shear Alfvén eigenmodes (RSAE) are the dominant instability. The real frequencies from all codes have a coefficient of variation of less than 5% for the most unstable modes with toroidal mode number n = 4 and 5. The simulated RSAE frequencies agree with experimental measurements if the minimum safety factor q min is adjusted, within experimental errors. The simulated growth rates exhibit greater variation, and simulations find that pressure gradients of thermal plasmas make a significant contribution to the growth rates. Mode structures of the dominant modes agree well among all codes. Moreover, using a calculated fast ion profile that takes into account the diffusion by multiple unstable modes, a toroidal Alfvén eigenmode (TAE) with n = 6 is found to be unstable in the outer edge, consistent with the experimental observations. Variations of the real frequencies and growth rates of the TAE are slightly larger than those of the RSAE. Finally, electron temperature fluctuations and radial phase shifts from simulations show no significant differences with the experimental data for the strong n = 4 RSAE, but significant differences for the weak n = 6 TAE. The verification and validation for the linear Alfvén eigenmodes is the first step to develop an integrated simulation of energetic particles confinement in burning plasmas incorporating multiple physical processes. Nuclear Fusion

The relative rates of the Rh(II)-mediated carbenoid insertion into the benzylic C−H bonds of a series of para-substituted phenyl substrates have been measured by an indirect intramolecular competition method. Three catalysts, rhodium(II) acetate, rhodium(II) trifluoroacetate, and rhodium(II) acetamide, were investigated. The effect of solvent was also studied on the reactions with rhodium(II) acetate as catalyst. The relative rates were analyzed by the Hammett equation. The relative rates are found to correlate better with σ than with σ+ for all three catalysts when CH2Cl2 is the solvent. For the insertion reactions catalyzed by Rh2(OAc)4, Rh2(O2CCF3)4, and Rh2(acam)4 in CH2Cl2, the Hammett correlations of the relative rates with σ give reaction constants of −1.26 (r = 0.98), −0.66 (r = 0.97), and −1.39 (r = 0.98), respectively. The Hammett analysis also indicates no significant solvent effect. The mechanistic significance of these Hammett correlations is discussed.

Global gyrokinetic particle simulations of electrostatic ion temperature gradient (ITG) instability show that the most unstable eigenmode is localized to some magnetic fieldlines or discrete locations on the poloidal plane in the Wendelstein 7-X (W7-X) stellarator due to its mirror-like magnetic fields, which vary strongly in the toroidal direction and induce coupling of more toroidal harmonics (n) to form the linear eigenmode than in the Large Helical Device (LHD) stellarator. Nonlinear electrostatic simulation results show that self-generated zonal flows are the dominant saturation mechanism for the ITG instabilities in both the LHD and W7-X. Furthermore, radial widths of the fluctuation intensity in both the LHD and W7-X are significantly broadened from the linear phase to the nonlinear phase due to turbulence spreading. Finally, nonlinear spectra in the W7-X are dominated by low-n harmonics, which can be generated both by nonlinear toroidal coupling of high-n harmonics and by linear toroidal coupling with large amplitude zonal flows due to the 3D equilibrium magnetic fields.