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161.
Oxidative Annulation of Arenecarboxylic and Acrylic Acids with Alkynes under Ambient Conditions Catalyzed by an Electron‐Deficient Rhodium(III) Complex 下载免费PDF全文
Eiji Kudo Dr. Yu Shibata Mutsumi Yamazaki Koji Masutomi Dr. Yuta Miyauchi Miho Fukui Haruki Sugiyama Prof. Dr. Hidehiro Uekusa Prof. Dr. Tetsuya Satoh Prof. Dr. Masahiro Miura Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14190-14194
It has been established that an electron‐deficient CpE rhodium(III) complex catalyzes the oxidative [4+2] annulation of substituted arenecarboxylic and acrylic acids with alkynes under ambient conditions (at RT–40 °C, under air) without using excess amounts of substrates to produce the corresponding substituted isocoumarins and α‐pyrones in high yields. Minor modification of reaction conditions depending on the coordination ability of alkynes realized the high efficiency. 相似文献
162.
Masahiro Kojima Prof. Dr. Motomu Kanai 《Angewandte Chemie (International ed. in English)》2016,55(40):12224-12227
Catalytic acceptorless dehydrogenation is an environmentally benign way to desaturate organic compounds. This process is traditionally accomplished with transition‐metal‐based catalysts. Herein, a borane‐catalyzed, metal‐free acceptorless dehydrogenation of saturated N‐heterocycles is disclosed. Tris(pentafluorophenyl)borane was identified as a versatile catalyst, which afforded several synthetically important N‐heteroarenes in up to quantitative yield. Specifically, the present metal‐free catalytic system exhibited a uniquely high tolerance toward sulfur functionalities, and demonstrated superior reactivity in the synthesis of benzothiazoles compared to conventional metal‐catalyzed systems. This protocol can thus be regarded as the first example of metal‐free acceptorless dehydrogenation in synthetic organic chemistry. 相似文献
163.
Nagamatsu S Misaki M Chikamatsu M Kimura T Yoshida Y Azumi R Tanigaki N Yase K 《The journal of physical chemistry. B》2007,111(17):4349-4354
Poly(2,5-dioctyloxy-1,4-phenylenevinylene) (DOPPV) was found to form a highly oriented film by a friction-transfer technique. Structural investigation of friction-transferred DOPPV was studied by means of polarized ultraviolet-visible (UV-vis) absorption spectroscopy, polarized photoluminescence (PL) spectroscopy, and synchrotron-sourced grazing incident X-ray diffraction (GIXD) analysis. The polarized UV-vis absorption and PL spectra indicate clear axial alignment. DOPPV backbones in friction-transferred film are highly aligned along the drawing direction of the friction-transfer. Further information of the molecular arrangement in friction-transferred DOPPV film was investigated by both the out-of-plane and the in-plane GIXD analyses with synchrotron source. The DOPPV molecules in friction-transferred films were perfectly arranged three-dimensionally: the backbones aligned along the drawing direction of friction-transfer, the alkyl side chains lay in the film plane, and the planar backbones were arranged parallel to the film surface. Additionally, two neighboring DOPPV molecules along the direction of inter-backbones separation by alkyl side chains were found to be shifted with respect to one another by the mean distance of half of a monomeric repeat. 相似文献
164.
Taniguchi S Kuroda K Doi K Tanabe M Shibata T Yoshida T Hatano T 《Chemical & pharmaceutical bulletin》2007,55(2):268-272
Gambir, the aqueous extract from Uncaria gambir (Rubiaceae), has been used as an astringent medicine in Asian countries. Investigation of the constituents in the extract led to the isolation of four chalcane-flavan dimers, gambiriin A1 (6), A2 (7), B1 (8), and B2 (9), in addition to (+)-catechin (1), (+)-epicatechin (2), and dimeric proanthocyanidins, procyanidin B1 (3), procyanidin B3 (4), and gambiriin C (5). The spectroscopic and chemical data obtained in the present study indicated that their previously proposed structures 6a, 7a, 8a, and 9a should be revised to 6, 7, 8, and 9, respectively. 相似文献
165.
166.
167.
Yang H Li H Wittenberg R Egi M Huang W Liebeskind LS 《Journal of the American Chemical Society》2007,129(5):1132-1140
alpha-Amino acid thiol esters derived from N-protected mono-, di-, and tripeptides couple with aryl, pi-electron-rich heteroaryl, or alkenyl boronic acids in the presence of stoichiometric Cu(I) thiophene-2-carboxylate and catalytic Pd(2)(dba)(3)/triethylphosphite to generate the corresponding N-protected peptidyl ketones in good-to-excellent yields and in high enantiopurity. Triethylphosphite plays a key role as a supporting ligand by mitigating an undesired palladium-catalyzed decarbonylation-beta-elimination of the alpha-amino thiol esters. The peptidyl ketone synthesis proceeds at room temperature under nonbasic conditions and demonstrates a high tolerance to functionality. 相似文献
168.
Six types of isoxazoles including 60 molecules were synthesized using combinatorial synthesis on solid support in a parallel fashion. Highly regioselective 1,3-dipolar cycloaddition of the nitrile oxides to the triple bond of the solid-attached ethynylbenzamides gave isoxazoles on solid support in good yield. Thirty molecules of them exhibited mesomorphic properties. The combination of molecular mechanics calculations and X-ray diffraction experiments of 2g and 3g revealed that the smectic phase of 2g had a bilayer structure, whereas 3g showed a monolayer liquid crystalline phase. These are supported in comparison with the single crystal structures of 2g and 3g. 相似文献
169.
An enantiospecific coupling of propargylic esters and carbonates with arylboronic acids has been developed using a palladium catalyst. Optically active 1,3-disubstituted allenes were synthesized with high enantiomeric excesses by carrying out the reactions under basic aqueous conditions. 相似文献
170.
The electronic structure of the lower states of a trigonal Cr3+ pair and Mo3+ pair, which occur in the Cs3M2Cl9 crystal (M=Cr,Mo), were studied by theoretical calculations carried out according to several methods: multireference singly and doubly excited configuration interaction, second-order configuration interaction, and multireference coupled-pair approximation. We employed a model of a [M2Cl9]3- anion embedded in a cage of point charges, which were arranged so as to simulate the anion in the crystal. The model core potential was utilized, where the relativistic effect was included for Mo. Results of the Cr complex showed that there were no direct bonds between the Cr metals. The lower electronic spectra of the [Cr2Cl9]3- ion were interpreted in terms of the electronic spectra of [CrCl6]3-. The lowest state of simultaneous excitation in both metals was considered. The [Mo2Cl9]3- ion exhibited a single direct bond between the metals. Reflecting this single bond, the observed singlet-triplet splitting was much larger than that in the case of Cr and the calculated splitting was in good agreement with the observed one. We account for the electronic spectra of the [Mo2Cl9]3- complex, which exhibited quite different features in the electronic excitation spectra in comparison with those of the Cr complex. 相似文献