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71.
Abstract The polymerizations of alkyl esters of propiolic acid by Rh complex catalysts were investigated. [Rh(norbornadiene)Cl]2, which was the most active among the catalysts examined, gave rise to poly(alkyl propiolate) in a fairly high yield (~80%) in the presence of alcohol as the polymerization solvent. The polymers formed were a pale yellow powder soluble in common organic solvents except for poly(methyl propiolate). The structures of the polymers obtained were investigated by IR, 13C-NMR, CP MAS 13C-NMR, and laser Raman spectroscopies, together with the x-ray diffraction method. Based on these spectroscopic data, it was concluded that this Rh complex can be called a stereoregular polymerization catalyst of alkyl propiolate because the poly(alkyl propiolate) obtained has a cis-transoidal structure. 相似文献
72.
Toyoji Kakuchi Toshifumi Satoh Junji Mata Satoshi Umeda Hisaho Hashimoto Kazuaki Yokota 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):325-336
Abstract The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF3OEt2 and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF3O-decyl2 comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl3, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs+ > Rb+ > K+ ? Na+ > Li+. The ratio of K+ and Na+, K+/Na+, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c. 相似文献
73.
The influence of electronic and steric effects of modified organoaluminum reagents to the stereoselectivity in the Diels-Alder and hetero-Diels-Alder reactions has been examined. 相似文献
74.
During the course of studies on butenolide synthesis1 we have investigated the utilities of 3-sulfur-functionalized propionic acid derivatives. We report the results with 3-carbanion species obtained from 3-phenylsulfiny1- and 3-phenylsulfonylpropionic acids (1) and (2). These compounds were easily prepared from 3-phenylthiopropionic acid. 相似文献
75.
76.
Toru Okawara Masaaki Abe Hisashi Shimakoshi Yoshio Hisaeda 《Research on Chemical Intermediates》2013,39(1):161-176
A Pd(II) complex, Pd(TPrPc-OH) (1, TPrPc-OH = 9-hydroxy-2,7,12,17-tetrapropylporphycenato dianion), has been synthesized and characterized. 1H NMR spectroscopy revealed that compound 1 exists as its enol form in solution. The H atom of the hydroxy group in 1 was exchanged with deuterium on addition of ethanol-d 6. UV–visible spectra showed a red shift of the Q band of 1 in THF compared with that of the acetoxy derivative Pd(TPrPc-OAc) (2, TPrPc-OAc = 9-acetoxy-2,7,12,17-tetrapropylporphycenato dianion). The pK a value of the hydroxy group in 1 was determined, by means of a UV–visible titration experiment, to be 10.56. A cyclic voltammogram of 1 in a mixture of THF and Britton–Robinson buffered aqueous solution revealed one-electron and one-proton coupled transfer in the oxidation process in the pH range from 2.7 to 10.5, which was identified by pH-varying experiments and the Pourbaix diagram. Transient absorption spectroscopy revealed that an electron-transfer reaction occurred from the triplet excited-state of 1 to 2,3,5,6-tetramethyl-1,4-benzoquinone (duroquinone, DQ) upon pulse laser irradiation at 532 nm. Such an intermolecular photoinduced electron-transfer reaction was not observed between the Ni analog, Ni(TPrPc-OH), and DQ. The reaction rate constant, k q, was indicative of a kinetic isotope effect with k q(H)/k q(D) = 1.7, supporting the belief that the exited-state electron transfer from 1 to DQ is accompanied by proton transfer. 相似文献
77.
Dr. Yuki Kishimoto Dr. Osamu Nakagawa Akane Fujii Dr. Kotaro Yoshioka Dr. Tetsuya Nagata Prof. Dr. Takanori Yokota Prof. Dr. Yoshiyuki Hari Prof. Dr. Satoshi Obika 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2427-2438
Artificial nucleic acids are widely used in various technologies, such as nucleic acid therapeutics and DNA nanotechnologies requiring excellent duplex-forming abilities and enhanced nuclease resistance. 2′-O,4′-C-Methylene-bridged nucleic acid/locked nucleic acid (2′,4′-BNA/LNA) with 1,3-diaza-2-oxophenoxazine (BNAP ( BH )) was previously reported. Herein, a novel BH analogue, 2′,4′-BNA/LNA with 9-(2-aminoethoxy)-1,3-diaza-2-oxophenoxazine (G-clamp), named BNAP-AEO ( BAEO ), was designed. The BAEO nucleoside was successfully synthesized and incorporated into oligodeoxynucleotides (ODNs). ODNs containing BAEO possessed up to 104-, 152-, and 11-fold higher binding affinities for complementary (c) RNA than those of ODNs containing 2′-deoxycytidine ( C ), 2′,4′-BNA/LNA with 5-methylcytosine ( L ), or 2′-deoxyribonucleoside with G-clamp ( PAEO ), respectively. Moreover, duplexes formed by ODN bearing BAEO with cDNA and cRNA were thermally stable, even under molecular crowding conditions induced by the addition of polyethylene glycol. Furthermore, ODN bearing BAEO was more resistant to 3′-exonuclease than ODNs with phosphorothioate linkages. 相似文献
78.
Tungsten‐Catalyzed Regio‐ and Enantioselective Aminolysis of trans‐2,3‐Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols 下载免费PDF全文
Dr. Chuan Wang Prof. Dr. Hisashi Yamamoto 《Angewandte Chemie (International ed. in English)》2014,53(50):13920-13923
The first catalytic enantioselective aminolysis of trans‐2,3‐epoxy alcohols has been accomplished. This stereospecific ring‐opening process was efficiently promoted by a tungsten/bis(hydroxamic acid) catalytic system, furnishing various anti‐3‐amino‐1,2‐diols with excellent regiocontrol and high enantioselectivities (up to 95 % ee). Moreover, virtually enantiopure 3‐amino‐1,2‐diols could be obtained by the sequential combination of two reactions that both involve the use of a chiral catalyst. 相似文献
79.
Satoshi Nagao Ayaka Suda Hisashi Kobayashi Naoki Shibata Yoshiki Higuchi Shun Hirota 《化学:亚洲杂志》2020,15(11):1743-1749
Domain swapping is an exception to Anfinsen's dogma, and more than one structure can be produced from the same amino acid sequence by domain swapping. We have previously shown that myoglobin (Mb) can form a domain‐swapped dimer in which the hinge region is converted to a helical structure. In this study, we showed that domain‐swapped dimerization of Mb was achieved by a single Ala mutation of Gly at position 80. Multiple Ala mutations at positions 81 and 82 in addition to position 80 facilitated dimerization of Mb by stabilization of the dimeric states. Domain swapping tendencies correlated well with the helical propensity of the mutated residue in a series of Mb mutants with amino acids introduced to the hinge region. These findings demonstrate that a single mutation in the hinge loop to modify helical propensity can control oligomer formation, providing new ideas to create high‐order protein oligomers using domain swapping. 相似文献
80.