A three-step methodology involving an external chiral ligand-mediated asymmetric addition of phenyllithium to an anisidine imine, oxidative removal of N-PMP group, and finally oxidative conversion of the phenyl group to a carboxyl group provides a facile synthesis of optically pure α-amino acid derivatives bearing a bulky α-substituent. 相似文献
Langmuir‐Blodgett films of a cellulose derivative containing porphyrins, porphyrin‐cellulose, were fabricated in order to construct a cellulose‐based molecular photocurrent generation system. On visible light illumination of the LB monolayer film deposited on an ITO electrode, anodic photocurrents were observed with a quantum yield of 1.6% at an applied potential of 0 V versus SCE, and 3.8–4.6% at 0.2–0.3 V versus SCE. These values indicate that the self‐quenching of the photoexcited porphyrins in the cellulose LB film was suppressed, while porphyrin moieties in the LB film had a densely packed structure. This is because the porphyrins are located at a distance of approximately 1.0 nm along the cellulose backbone.
Highly diastereoselective tandem alkylation process of acyclic α,β-unsaturated esters was developed based on the novel use of dithioacetal as a stereocontrolling unit. 相似文献
Organic dye particles of micrometer and submicrometer diameters were prepared by a wetting/dewetting procedure on a hydrophilic glass surface and a self-organized one- or two-dimensional registration was observed. To analyze the molecular assembly in these particles the near-field-excited near-field fluorescence from single particles were detected, while the majority of particles with diameters around 2 μm or less did not show fluorescence. Far-field fluorescence, in contrast, was observed for every particle, and the intensity depended on the excitation polarization when a polarized evanescent field was used for excitation, indicating that the molecules’ transition moment within dye particles orient parallel to the substrate surface. These two observations suggest that the near-field at the tip of the probe was polarized parallel to the probe axis. Another observation, that neighboring particles show similar molecular orientations, suggests that the dewetting process contributed to the alignment of the molecular directions in adjacent particles, which further proves that the dye particles were formed by a self-organizing mechanism. 相似文献
Benzylchlorocarbenes generated photolytically from diazirines in EtOH afford chlorostyrenes and acetals, whose distributions are sensitive to the reaction temperature. 相似文献
To show that persistent high-spin polycarbenes can be realized by utilizing hetero spin systems, two diphenyldiazomethanes having pyridyl groups, i.e., bis{4-(4-pyridyl)-2,6-dimethylphenyl}diazomethane (4,4'-DPy-1-N(2)) and {2,4-di(4-pyridyl)-6-bromophenyl}(2,6-dimethyl-4-tert-butylphenyl)diazomethane (2,4-DPy-1-N(2)), were prepared. Triplet carbenes, 4,4'-DPy-1 and 2,4-DPy-1, generated by photolysis of the corresponding diazomethanes were characterized by spectroscopic means (ESR and UV/vis in matrix at low temperatures and laser flash photolysis in solution at room temperature). The results showed that they were fairly persistent. Magnetic properties of the photoproducts from a 1:1 complex between DPy-1-N(2) and Cu(hfac)(2) (hfac = hexafluoroacetylacetonate) were characterized by ESR and a superconducting quantum interference device (SQUID) magneto/susceptometer. The field dependences of magnetization for the complexes, expressed by using M versus H/T plots, were analyzed in terms of the Brillouin function to be S = 6.80 (F = 0.60) for the 1:1 complex of 4,4'-DPy-1 and Cu(hfac)(2) and S = 3.71 (F = 0.73) for the 1:1 complex of 2,4-DPy-1 and Cu(hfac)(2) at 2.0 K. Thus, it has been demonstrated that a high-spin species is actually generated in the photoproducts and that the complexed carbenes showed significant stability. 相似文献
Novel cellobiose and cellulose (DPn=ca. 30) derivatives, N-(1-pyrenebutyloyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (6), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (7), N-(1-pyrenebutyloyl)-β-cellulosylamine (13), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-β-cellulosylamine (14) carrying a pyrene group as a single fluorescent probe at the reducing end, were prepared in order to investigate their self-assembly systems in solutions. The relative intensity of the excimer emission at ca. 480 nm due to dimerized pyrenes (intensity IE) to the monomer emission at ca. 380 nm due to isolated pyrene (intensity IM), i.e., IE/IM, was monitored in various solutions. In water/dimethyl sulfoxide (DMSO) mixed solvent (0–98%, v/v), the ratio IE/IM remained low (0.04) for compound 6 over the range of water concentrations, indicating that pyrenes at C-1 position of compound 6 were diffused. On the other hand, the ratio IE/IM increased (0.04–4.96) for compound 7 with the increase in water concentration, indicating that pyrenes at C-1 position were associated. In aqueous NaOH solutions (4.4–17.5%, w/w), compound 14 showed a large increase in the ratio IE/IM (0.84–8.14) with the increase in NaOH concentration, compared to compound 13 (0.06–0.41). It was found that the association of hydrophobic groups at the reducing-end of cellulose could be controlled by the hydrophilic–hydrophobic balance of compounds and the solvent polarity. 相似文献