Atropodiastereoselective 5N-Acylation of 1,5-Benzodiazepin-2-ones with (S)-2-Phenylpropanoyl and (S)-2-Phenylbutanoyl Chlorides.

5N-Acylation of 1N-methyl-1,5-benzodiazepin-2-ones with (S)-2-phenylpropanoyl and (S)-2-phenylbutanoyl chlorides afforded the (a1S,a2S,S)-atropisomer (I) diastereoselectively over the (a1R,a2R,S)-isomer (II) in the ratio of 1:0.06-0.15. The preferential formation of I may be explained by the thermodynamically preferable π-π stacking interaction between two benzene rings in the benzodiazepine ring and the acyl chloride during the reaction. Analysis using ab initio calculations (RI-MP2/6-31+G(d) level of theory) for the acylation reaction indicated the π-π stacking interaction in the transition state. Furthermore, isomer I was shown to be thermodynamically more stable than II. The higher stability of I may be caused by the folded form of the two benzene rings, which was revealed by NMR, X-ray, and computational analyses.

Nanoporous GaN onp-type GaN: a Mg out-diffusion compensation layer for heavily Mg-dopedp-type GaN.

Embeddingp-type gallium nitride (p-GaN) with controlled Mg out-diffusion in adjacent epitaxial layers is a key for designing various multi-junction structures with high precision and enabling more reliable bandgap engineering of III-nitride-based optoelectronics and electronics. Here, we report, for the first time, experimental evidence of how nanoporous GaN (NP GaN) can be introduced as a compensation layer for the Mg out-diffusion fromp-GaN. NP GaN onp-GaN provides anex-situformed interface with oxygen and carbon impurities, compensating for Mg out-diffusion fromp-GaN. To corroborate our findings, we used two-dimensional electron gas (2DEG) formed at the interface of AlGaN/GaN as the indicator to study the impact of the Mg out-diffusion from underlying layers. Electron concentration evaluated from the capacitance-voltage measurement shows that 9 × 1012cm-2of carriers accumulate in the AlGaN/GaN 2DEG structure grown on NP GaN, which is the almost same number of carriers as that grown with nop-GaN. In contrast, 2DEG onp-GaN without NP GaN presents 9 × 109cm-2of the electron concentration, implying the 2DEG structure is depleted by Mg out-diffusion. The results address the efficacy of NP GaN and its' role in successfully embeddingp-GaN in multi-junction structures for various state-of-the-art III-nitride-based devices.