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171.
Bond IA Budding E Conway MJ Fenton KB Fujii H Fujii Z Hasegawa H Hayashida N Honda M Hotta N Humble JE Kabe S Kasahara K Kifune T Masaike A Matsubara Y Mitsui K Miura Y Mori M Murakami K Muraki Y Nagano M Nakamura K Nakamura T Norris PM Ohashi Y Okada A Saito T Sakata M Sato H Shibata S Shima M Storey JR Tanimori T Teshima M Torii S Uchino K Watase Y Woodhams MD Yamamoto Y Yock PC Yuda T 《Physical review letters》1988,60(12):1110-1113
172.
Aika Takeshima Prof. Dr. Taichi Kano 《Angewandte Chemie (International ed. in English)》2023,62(8):e202217496
A novel route to synthesize 1,4-dicarbonyl compounds is described. α,α-Dibromoketones generate zinc enolates through a diethylzinc-mediated halogen-metal exchange and react with α-bromocarbonyl compounds to furnish 1,4-dicarbonyl compounds via a second generation of zinc enolates. This cross-coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α-dibromoketones in the presence of α-bromocarbonyl compounds. Chiral 1,4-dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes using a chiral secondary amine catalyst and a subsequent cross-coupling reaction between the resulting chiral α-bromoaldehydes and α,α-dibromoacetophenones. 相似文献
173.
Saori Tsuzuki Prof. Dr. Taichi Kano 《Angewandte Chemie (International ed. in English)》2023,62(16):e202300637
Chiral sulfimides, the aza-analogues of sulfoxides, are valuable compounds in organic synthesis and medicinal chemistry. Herein, we report an efficient method for preparing chiral sulfimides from easily available enantioenriched sulfinamides. The key step of this method is a stereospecific oxygen-selective alkylation of enantioenriched sulfinamides, which is accomplished by using isopropyl iodide, K2CO3, and DMPU. The resulting chiral sulfinimidate esters are transformed to chiral sulfimides by the nucleophilic addition of the Grignard reagents under simple conditions. This transformation enables access to the enantioenriched diaryl or dialkyl sulfimides bearing two similar carbon substituents, which are difficult to synthesize by previous methods. 相似文献
174.
Hoshi T Nakazawa T Saitoh I Mori A Suzuki T Sakai J Hagiwara H 《Organic letters》2008,10(10):2063-2066
High activity in the palladium-catalyzed Suzuki-Miyaura reactions of aryl chlorides with arylboronic acids was furnished using biphenylene-substituted di- tert-butylruthenocenylphosphine (R-Phos) as a supporting ligand. Substrate combinations even for the construction of highly hindered tetra- ortho-substituted biaryls can be achieved in good to excellent yields with low catalyst loadings in short reaction times. 相似文献
175.
Masakatsu Matsumoto Masatoshi Tanimura Taichi Akimoto Nobuko Watanabe Hisako K. Ijuin 《Tetrahedron letters》2008,49(26):4170-4173
An aprotic polar solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic polar solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene. 相似文献
176.
Taichi Kano 《Tetrahedron letters》2008,49(37):5369-5371
A binaphthyl-based amino sulfonamide (S)-2 was applied to the direct asymmetric aminoxylation of aldehydes with nitrosobenzene. The reaction catalyzed by (S)-2 proceeded smoothly to give the aminoxylated product in good yield with excellent enantioselectivity. This method represents a rare example of the highly enantioselective aminoxylation by a non-proline type catalyst with high catalytic performance. 相似文献
177.
The electronic structures and structural morphologies of naphthalene cluster anions, (naphthalene)(n)(-) (n=3-150), and its related aromatic cluster anions, (acenaphthene)(n)(-) (n=4-100) and (azulene)(n)(-) (n=1-100), are studied using anion photoelectron spectroscopy. For (naphthalene)(n) (-) clusters, two isomers coexist over a wide size range: isomers I and II-1 (28 < or = n < or =60) or isomers I and II-2 (n > or = ~60). Their contributions to the photoelectron spectra can be separated using an anion beam hole-burning technique. In contrast, such an isomer coexistence is not observed for (acenaphthene)(n) (-) and (azulene)(n) (-) clusters, where isomer I is exclusively formed throughout the whole size range. The vertical detachment energies (VDEs) of isomer I (7 < or = n < or = 100) in all the anionic clusters depend linearly on n(-13) and their size-dependent energetics are quite similar to one another. On the other hand, the VDEs of isomers II-1 and II-2 produced in (naphthalene)(n)(-) clusters with n > or = approximately 30 remain constant at 0.84 and 0.99 eV, respectively, 0.4-0.6 eV lower than those of isomer I. Based upon the ion source condition dependence and the hole-burning photoelectron spectra experiments for each isomer, the energetics and characteristics of isomers I, II-1, and II-2 are discussed: isomer I is an internalized anion state accompanied by a large change in its cluster geometry after electron attachment, while isomers II-1 and II-2 are crystal-like states with little structural relaxation. The nonappearance of isomers II-1 and II-2 for (acenaphthene)(n)(-) and (azulene)(n)(-) and a comparison with other aromatic cluster anions indicate that a highly anisotropic and symmetric pi-conjugated molecular framework, such as found in the linear oligoacenes, is an essential factor for the formation of the crystal-like ordered forms (isomers II-1 and II-2). On the other hand, lowering the molecular symmetry makes their production unfavorable. 相似文献
178.
A direct asymmetric iodination reaction of aldehydes with NIS was found to be catalyzed by the novel axially chiral bifunctional amino alcohol (S)-1d. This method represents the rare example of the catalytic and highly enantioselective synthesis of optically active alpha-iodoaldehydes. 相似文献
179.
Kusakabe T Kato K Motodate S Takaishi S Akita H 《Chemical & pharmaceutical bulletin》2008,56(10):1436-1437
A total synthesis of (+)-bakkenolide-A was carried out via the key intermediate 4, which was prepared based on an asymmetric cyclization-carbonylation reaction established in our laboratory. Diastereoselective construction of the spirolactone moiety was achieved using Mitsuhashi's protocol as a key step. 相似文献
180.
Mass spectrometry and photoelectron spectroscopy of o-, m-, and p-terphenyl cluster anions, (o-TP)n(-) (n = 2-100), (m-TP)n(-) (n = 2-100), and (p-TP)n(-) (n = 1-100), respectively, are conducted to investigate the effect of molecular shape on the molecular aggregation form and the resultant ion core character of the clusters. For (o-TP)n(-) and (m-TP)n(-), neither magic numbers nor discernible isomers are observed throughout the size range. Furthermore, their vertical detachment energies (VDEs) increase up to large n and depend linearly on n(-1/3), implying that they possess a three-dimensional (3D), highly reorganized structure encompassing a monomeric anion core. For (p-TP)n(-), in contrast, prominent magic numbers of n = 5, 7, 10, 12, and 14 are observed, and the VDEs show pronounced irregular shifts below n = 10, while they remain constant above n = 14 (isomer A). These results can be rationalized with two-dimensional (2D) orderings of p-TP molecules and different types of 2D shell closure at n = 7 and 14, the monomeric and multimeric anion core, respectively. Above n = 16, the new feature (isomer B) starts to appear at the higher binding side of isomer A, and it becomes dominant with n, while isomer A gradually disappears for larger sizes. In contrast to isomer A, the VDEs of isomer B continuously increase with the cluster size. This characteristic size evolution suggests that the transition to modified 2D aggregation forms from 2D ones occurs at around n = 20. 相似文献