Pd-catalyzed asymmetric allylic amination of Morita-Baylis-Hillman adduct derivatives using chiral diaminophosphine oxides: DIAPHOXs

[reaction: see text] Asymmetric allylic amination of allylic carbonates prepared from racemic Morita-Baylis-Hillman adducts proceeded in the presence of Pd catalyst, chiral diaminophosphine oxide (DIAPHOX), and BSA, affording the corresponding chiral aza-Morita-Baylis-Hillman adduct derivatives in excellent yield with up to 99% ee. The cyclic reaction products could be converted into various synthetically useful compounds such as chiral cyclic beta-amino acids.     

Synthesis, structural transformation, thermal stability, valence state, and magnetic and electronic properties of PbNiO3 with perovskite- and LiNbO3-type structures

We synthesized two high-pressure polymorphs PbNiO(3) with different structures, a perovskite-type and a LiNbO(3)-type structure, and investigated their formation behavior, detailed structure, structural transformation, thermal stability, valence state of cations, and magnetic and electronic properties. A perovskite-type PbNiO(3) synthesized at 800 °C under a pressure of 3 GPa crystallizes as an orthorhombic GdFeO(3)-type structure with a space group Pnma. The reaction under high pressure was monitored by an in situ energy dispersive X-ray diffraction experiment, which revealed that a perovskit-type phase was formed even at 400 °C under 3 GPa. The obtained perovskite-type phase irreversibly transforms to a LiNbO(3)-type phase with an acentric space group R3c by heat treatment at ambient pressure. The Rietveld structural refinement using synchrotron X-ray diffraction data and the XPS measurement for both the perovskite- and the LiNbO(3)-type phases reveal that both phases possess the valence state of Pb(4+)Ni(2+)O(3). Perovskite-type PbNiO(3) is the first example of the Pb(4+)M(2+)O(3) series, and the first example of the perovskite containing a tetravalent A-site cation without lone pair electrons. The magnetic susceptibility measurement shows that the perovskite- and LiNbO(3)-type PbNiO(3) undergo antiferromagnetic transition at 225 and 205 K, respectively. Both the perovskite- and LiNbO(3)-type phases exhibit semiconducting behavior.     

An approach to control of band gap energy and photoluminescence upon band gap excitation in Pr(3+)-doped perovskites La(1/3)MO3 (M=Nb, Ta):Pr3+

We synthesized polycrystalline pristine and Pr(3+)-doped perovskites La(1/3)MO(3) (M = Nb, Ta):Pr(3+) and investigated their crystal structure, optical absorption, and luminescence properties. The optical band gap of La(1/3)NbO(3) (3.2 eV) is smaller than that of La(1/3)TaO(3) (3.9 eV), which is primarily due to the difference in electronegativity between Nb and Ta. In La(1/3)NbO(3):Pr(3+), the red emission assigned to the f-f transition of Pr(3+) from the excited (1)D(2) level to the ground (3)H(4) state upon band gap photoexcitation (near-UV) was observed, whereas the f-f transition of Pr(3+) with blue-green emission from the excited (3)P(0) level to the ground (3)H(4) state was quenched. On the other hand, in La(1/3)TaO(3):Pr(3+), the blue-green emission upon band gap photoexcitation was observed. Their differences in emission behavior are attributed to the energy level of the ground and excited states of 4f(2) for Pr(3+), relative to the energy levels of the conduction and valence bands, and the trapped electron state, which mediates the relaxation of electron from the conduction band to the excited state of Pr(3+). La(1/3)NbO(3):Pr(3+) is a candidate red phosphor utilizing near-UV LED chips (e.g., λ = 375 nm) as an excitation source.     

Novel chiral hydrogen bond donor catalysts based on a 4,5-diaminoxanthene scaffold: application to enantioselective conjugate addition of 1,3-dicarbonyl compounds to nitroalkenes

Novel chiral hydrogen bond donor catalysts based on a 4,5-diamino-9,9′-dimethylxanthene skeleton were designed and synthesized. Among the phenylurea-amide hybrid molecules prepared from various natural/unnatural chiral amino acids, the phenylalanine-derived catalyst, and the proline-derived catalyst were successfully applied to enantioselective conjugate addition of 1,3-dicarbonyl compounds to nitroalkenes. Using 2-acetylcyclopentanone and 2-methoxycarbonylcyclopentanone as prochiral nucleophiles, asymmetric conjugate addition to β-aryl nitroalkenes proceeded with good diastereoselectivity to provide the corresponding products bearing an all-carbon quaternary stereocenter in excellent yield with up to 95% ee.     

大鼠中风模型的超小氧化铁粒子神经血管成像(英文)

现今诱导血管增生剂在中风后的治疗效应引起了人们的关注.这项工作的一个目的是用短时脑中动脉栓塞大鼠中风模型(MCAO)和磁化率加权成像(SWI)的核磁共振成像(MRI)方法,监测在中风后半月形损伤区新生成的旁侧血管.P904是法国格尔伯实验室生产的超小超顺磁氧化铁粒子弛豫试剂(USPIO).它在低剂量减少T1弛豫时间,适中剂量时减少T2*弛豫时间.实验动物被随机分为3组:中风Sildenafil治疗组(n=6)、中风无治疗对照组(n=5)和无中风无治疗对照组(n=1).在P904注入前后分别进行MRI成像.磁化率加权成像的时间点是:栓塞手术前、栓塞手术后24小时、栓塞手术后两周和四周.结果表明,术后两周,在治疗组中中风严重的动物的缺血区的周边显示了MRI可见的新生血管.结论:在短时脑中动脉栓塞大鼠中风模型中,使用超小超顺磁氧化铁粒子弛豫试剂和7 T高分辨磁化率加权成像能够监测半月形损伤区新生血管的形成.     

Synthesis of fused-tricyclic indole derivatives through an acid-promoted skeletal rearrangement

We developed a novel method for synthesizing fused-tricyclic indole derivatives with a 3-aminomethyl indole motif through a reaction cascade involving ipso-Friedel–Crafts alkylation of phenols, rearomatization of the spirocyclohexadienone unit, and iso-Pictet–Spengler reaction. Using TFA as an acid promoter, six-, seven-, and eight-membered ring-fused indoles were obtained in 31–99% yield.