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81.
82.
Chemoselective and Direct Functionalization of Methyl Benzyl Ethers and Unsymmetrical Dibenzyl Ethers by Using Iron Trichloride 下载免费PDF全文
Dr. Yoshinari Sawama Ryota Goto Saori Nagata Yuko Shishido Dr. Yasunari Monguchi Prof. Dr. Hironao Sajiki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2631-2636
Methyl and benzyl ethers are widely utilized as protected alcohols due to their chemical stability, such as the low reactivity of the methoxy and benzyloxy groups as leaving groups under nucleophilic conditions. We have established the direct azidation of chemically stable methyl and benzyl ethers derived from secondary and tertiary benzyl alcohols. The present azidation chemoselectively proceeds at the secondary or tertiary benzylic positions of methyl benzyl ethers or unsymmetrical dibenzyl ethers and is also applicable to direct allylation, alkynylation, and cyanation reactions, as well as the azidation. The present methodologies provide not only a novel chemoselectivity but also the advantage of shortened synthetic steps, due to the direct process without the deprotection of the methyl and benzyl ethers. 相似文献
83.
Dr. Yoshinari Sawama Yuko Shishido Takahiro Kawajiri Ryota Goto Dr. Yasunari Monguchi Prof. Dr. Hironao Sajiki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(2):510-516
Friedel–Crafts benzylations between unactivated arenes and benzyl alcohol derivatives are clean and straightforward processes to construct biologically useful di‐ and tri‐arylmethanes. We have established an efficient iron‐catalyzed Friedel–Crafts benzylation method at room temperature that uses benzyl TMS ethers as substrates, which are poorly reactive under common nucleophilic substitution conditions. The reaction seems to progress through iron‐catalyzed self‐condensation of the benzyl TMS ether to the corresponding dibenzylic ether. The use of excess arene relative to benzyl TMS ether produced mono‐benzylated arene (di‐ and tri‐arylmethane products), whereas the use of excess benzyl TMS ether versus arene provided bis‐benzylated arene (polyarylated products) in high yields and regioselectivities. In previous methods, the latter double Friedel–Crafts benzylations hardly proceed. 相似文献
84.
Daiki Minamida Shusuke Okada Mineo Hashizume Yoshihiro Sasaki Jun-ichi Kikuchi Nobuyoshi Hosoito Toru Imori 《Journal of Sol-Gel Science and Technology》2008,48(1-2):95-101
Magnetic cerasome, an artificial cell membrane having ultrathin magnetic metal layers on the surface, was prepared through electroless plating of magnetic metal alloy onto an organic–inorganic vesicular nanohybrid “cerasome.” Morphological and functional characteristics of the magnetic cerasome were evaluated using various physical measurements: scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, electron tomography, and vibrating sample magnetometry. The results proved that high morphological stability of the cerasome was important for constructing the magnetic lipid vesicle and that insertion of an alkylated metal ligand into the cerasome was essential to the magnetic metal alloy deposition on the cerasome surface. Fluorescence microscopic observations revealed that the magnetic cerasomes were collected reversibly on the slide glass surface and manipulated depending on external motion of a magnet. The potential use of the magnetic cerasomes as a novel vesicular nanohybrid is also described in this report. 相似文献
85.
86.
Negative-mode matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) analysis of industrial pigments was performed using tetrathiafulvalene (TTF), an electron donating compound, as a matrix. Comparing with other matrices such as tetracyanoquinodimethane (TCNQ), dithranol, 2-hydroxy-6-nitroaniline (HNA), and harmine hydrochloride, the most abundant analyte ions were produced by the TTF as radical or deprotonated anions. In addition, fragment ions in the negative mode of operation are also found to be much less abundant than those in the positive mode of operation. 相似文献
87.
Daiki Monguchi Daisuke Hashizume Mikiko Sodeoka 《Journal of organometallic chemistry》2008,693(5):867-873
We describe herein the catalytic asymmetric conjugate reduction of α,β-unsaturated carbonyl compounds using a novel cationic Pd-iPr-DUPHOS complex. In this reaction, EtOH worked well as a solvent and a reducing agent, and the reaction was completed within several hours in most cases to afford the reduced compounds almost quantitatively with modest to good enantioselectivity (up to 72% ee). It was found that the Pd-iPr-DUPHOS complex was more reactive than the previously reported Pd-BINAP complex when molecular sieves 4A was added as an additive. Based on an X-ray structural analysis of [Pd{(S,S)-iPr-duphos}](OTf)2 complex, a working hypothesis of the reaction mechanism is also described. 相似文献
88.
Systemically Injectable Enzyme‐Loaded Polyion Complex Vesicles as In Vivo Nanoreactors Functioning in Tumors 下载免费PDF全文
Dr. Yasutaka Anraku Dr. Akihiro Kishimura Dr. Mako Kamiya Dr. Sayaka Tanaka Dr. Takahiro Nomoto Dr. Kazuko Toh Dr. Yu Matsumoto Shigeto Fukushima Daiki Sueyoshi Prof. Mitsunobu R. Kano Prof. Yasuteru Urano Prof. Nobuhiro Nishiyama Prof. Kazunori Kataoka 《Angewandte Chemie (International ed. in English)》2016,55(2):560-565
The design and construction of nanoreactors are important for biomedical applications of enzymes, but lipid‐ and polymeric‐vesicle‐based nanoreactors have some practical limitations. We have succeeded in preparing enzyme‐loaded polyion complex vesicles (PICsomes) through a facile protein‐loading method. The preservation of enzyme activity was confirmed even after cross‐linking of the PICsomes. The cross‐linked β‐galactosidase‐loaded PICsomes (β‐gal@PICsomes) selectively accumulated in the tumor tissue of mice. Moreover, a model prodrug, HMDER‐βGal, was successfully converted into a highly fluorescent product, HMDER, at the tumor site, even 4 days after administration of the β‐gal@PICsomes. Intravital confocal microscopy showed continuous production of HMDER and its distribution throughout the tumor tissues. Thus, enzyme‐loaded PICsomes are useful for prodrug activation at the tumor site and could be a versatile platform for enzyme delivery in enzyme prodrug therapy. 相似文献
89.
meso‐Nitro‐ and meso‐Aminosubporphyrinatoboron(III)s and meso‐to‐meso Azosubporphyrinatoboron(III)s 下载免费PDF全文
Daiki Shimizu Seung‐Kyu Lee Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《化学:亚洲杂志》2016,11(20):2946-2952
meso‐Nitrosubporphyrinatoboron(III) was synthesized by nitration of meso‐free subporphyrin with AgNO2/I2. The subsequent reduction with a combination of NaBH4 and Pd/C gave meso‐aminosubporphyrinatoboron(III). meso‐Nitro‐ and meso‐amino‐groups significantly influenced the electronic properties of subporphyrin, which has been confirmed by NMR and UV/Vis spectra, electrochemical analysis, and DFT calculations. Oxidation of meso‐aminosubporphyrinatoboron(III)s with PbO2 cleanly gave meso‐to‐meso azosubporphyrinatoboron(III)s that exhibited almost coplanar conformations and large electronic interaction through the azo‐bridge. 相似文献
90.
Studies of the Electronic Effects of Zinc Cluster Catalysts and Their Application to the Transesterification of β‐Keto Esters 下载免费PDF全文
Dr. Kazushi Agura Dr. Yukiko Hayashi Mari Wada Daiki Nakatake Prof. Dr. Kazushi Mashima Prof. Dr. Takashi Ohshima 《化学:亚洲杂志》2016,11(10):1548-1554
The electronic effects of tetranuclear zinc cluster catalysts on transesterification were investigated by changing the carboxylate ligands in the clusters. High catalyst activity crucially depended on the balance between Lewis acidity and Brønsted basicity of the catalyst; this was consistent with the dual activation of both the electrophile and nucleophile by the cooperative zinc centers. In addition, tetranuclear zinc cluster catalysts achieved the transesterification of β‐keto esters with unprecedented levels of broad substrate generality, in which a newly developed pentafluoropropionate‐bridged zinc cluster and 4‐dimethylaminopyridine additive greatly improved the reactivity of sterically congested α‐ and α,α‐disubstituted β‐keto esters. 相似文献