The regioselective anti-carboindation of ynamides by using InBr3 and silylated nucleophiles was developed to synthesize (Z)-β-(carbonylamino)alkenylindiums. The X-ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti-addition fashion. In contrast to reported syn-carbometalations of ynamides by using organometallics, a cooperation of InBr3 and silylated nucleophiles to ynamides achieved an anti-addition, which was supported by DFT calculations. The scope of substrates included various ynamides and silylated nucleophiles, such as silyl ketene acetals and silyl ketene imines. The transformation of synthesized alkenylindiums by iodination, radical coupling, and Pd-catalyzed cross-coupling successfully afforded trisubstituted enamines with high regio- and stereoselectivities. 相似文献
The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO2 film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO2. By TiO2 photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO2 photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO2. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO2 photocatalyst were elucidated.
Organogallium and ‐indium compounds are useful reagents in organic synthesis because of their moderate stability, efficient reactivity and high chemoselectivity. Carbogallation and ‐indation of a carbon‐carbon multiple bond achieves the simultaneous formation of carbon‐carbon and carbon‐metal bonds. Heterogallation and ‐indation construct carbon‐heteroatom and carbon‐metal bonds. Therefore, these reaction systems represent a significant synthetic method for organogalliums and ‐indiums. Many chemists have attempted to apply various types of unsaturated compounds such as alkynes, alkenes, and allenes to these reaction systems. This minireview provides an overview of carboindation and ‐gallation as well as heteroindation and ‐gallation. 相似文献
The steady-state and time-resolved fluorescece spectroscopy is one of the most powerful method to detect and analyze subtle
conformation change and interaction between peptide elements in protein. Phytocystatin Scb isolated from sunflower seeds includes
a single Trp residue at position 85. In an attempt to investigate the interaction of the N-terminal region of Scb with the
first and second hairpin loops by fluorescence spectroscopy of Trp residue, two Scb mutants in which single Trp locates at
position 52 and 58, respectively, and their N-terminal removed mutants were generated. The N-terminal truncation changed the
fluorescence decay kinetics of Trp52 from the triple exponential to double. Furthermore, the time-resolved fluorescence anisotropy
residue indicated that the segmental motion of Trp52 was significantly enhanced by its N-terminal truncation. In contrast,
Trp58 and Trp85 had little influence. The N-terminal successive truncations of Scb and its mutants resulted in the weaken
inhibitors to papain. These results suggested that the N-terminal region of Scb interacts with the peptide segment preceding
the first hairpin loop, thereby stabilizing the conformation of the hairpin loop structure. 相似文献
The coupling reactions of alkyl chlorides with silyl enolates catalyzed by InBr3, and the coupling reactions of alkyl ethers with silyl enolates catalyzed by the combined Lewis acid of InBr3/Me3SiBr are described. In both reaction systems, various types of silyl enolates were used to give corresponding α-alkylated esters, ketones, carboxylic acids, amides, thioesters, and aldehydes. 相似文献
In various trials for elucidating the physiological function of pokeweed antiviral protein (PAP), studies on the interaction with sugar are essential. The fluorescence titration curves showed that PAP retained the strong affinity against N-acetylglucosamine (NAG) and two sites in one PAP molecule co-operatively participated in the binding. In the complex of PAP with NAG, Trp208 located at the entrance lid site of substrate came closer to Tyr72 about 0.3 Å. Furthermore, the fluorescence anisotropy decay measurement demonstrated that the segmental rotation of Trp208 was enlarged by the binding of PAP with NAG. Such conformational changes around the active site closely correlate with the enzymatic activity of PAP. The N-glycosidase activity of PAP was enhanced more than two times in the presence of NAG. The obtained results consistently suggested the enzymatic activity of PAP would be regulated through the conformation change near the active site induced by the binding with NAG. 相似文献
Hydrogenated amorphous-Si/SiO2 (a-Si:H/SiO2) superlattices with different a-Si : H thickness in the range of a few nanometers have been fabricated by ultra high vacuum evaporator (UHV evaporator). The photoluminescence (PL) of our superlattices is observed in the visible spectral region and the peak energy shifts to higher energy as the a-Si : H layer thickness decreases. The temperature dependence of the PL spectra reveals four sub-bands by fitting. Bands at 2.2, 1.9, 1.65 and 1.45 eV are detected and are attributed to E′δ centers, nonbridging-oxygen–hole centers (NBOHC), Si/SiO2 interface and a-Si : H layer, respectively. We explain the overall blueshift of the PL spectra by the modification of the contribution of these sub-bands. 相似文献
The chiral Br?nsted acid (1b or 1c) has been shown to initiate the Hosomi-Sakurai reaction of imines with excellent enantioselectivities. The combined Br?nsted acid system has been developed to offer a new class of chiral Br?nsted acid catalysis. The present system proceeds through regeneration of the chiral Br?nsted acid by proton transfer from additional Br?nsted acid to silylated chiral Br?nsted acid, a newly elucidated mechanism for the role of the additional Br?nsted acid. 相似文献