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1.
Koichi Itoh Takeji Takui 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2004,80(2):29
This review paper deals with an overview of molecule-based magnetism as a rapidly developing interdisciplinary field, topological symmetry rule as the first principle of spin alignment in organic open-shell systems in the ground state, the proposal of organic through-bond 1D and 2D ferro- and superparamagnets and the detection of the first organic high-spin molecule, m-phenylenebis(phenylmethylene) in the quintet ground state (S = 2), followed by extended organic high-spin systems with π-conjugation such as aromatic hydrocarbons having S = 3, 4, 5. The paper also describes a theoretical approach to the understanding of electronic spin structures of organic high-spin molecules by invoking both Heisenberg and Hubbard model Hamiltonians, weakly interacting intramolecular high-spin systems from both experimental and theoretical sides, the spin density distribution of the first organic high-spin molecule in terms of electron- nuclear multiple resonance spectroscopy and the detection and characterization of ionic high-spin hydrocarbons, emphasizing the establishment of high spin chemistry underlying organic molecular magnetism. 相似文献
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The enantio-controlled synthesis of trans-4,5-benzhydrindan-1-ones was achieved by means of a stereoselective [4+2] cycloaddition of o-quinodimethanes generated by a thermal cleavage of benzocyclobutene derivatives as a key step. The chiral substrates of the thermal reaction were synthesized by a diastereoselective Grignard addition to the chiral O-isopropylideneglyceroketones connected to a benzocyclobutene ring, which were simply prepared from D-mannitol as a chiral source. This approach can provide a new efficient access to A-nor B-aromatic steroidal compounds. 相似文献
4.
Akiko Sekihara Hidekazu Honma Tadahiro Fukuju Kiminori Maeda Hisao Murai 《Research on Chemical Intermediates》1998,24(8):859-877
Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied
by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems
(methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration
conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical
pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E
pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that
the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign
of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in
the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles
in thermal equilibrium. 相似文献
5.
Morita Y Murata T Fukui K Yamada S Sato K Shiomi D Takui T Kitagawa H Yamochi H Saito G Nakasuji K 《The Journal of organic chemistry》2005,70(7):2739-2744
[structure: see text] Novel hydrogen-bonded charge-transfer salts of TCNQ with mono- and diprotonated 4,4'-biimidazolium were synthesized in order to demonstrate the high potential of the 4,4'-biimidazole system in a molecular conductor from the viewpoint of crystal engineering and electronic modulation. Crystal structure analyses of neutral 4,4'-biimidazole and TCNQ salts revealed the formation of two types of hydrogen-bonding modes of the 4,4'-biimidazole moiety depending on the protonated states. Neutral 4,4'-biimidazole possessed a linear chain mode of hydrogen-bonding to construct two-dimensional network. In the TCNQ salt of monoprotonated 4,4'-biimidazolium, the 4,4'-biimidazole moiety formed a dimer by a complementary mode of hydrogen-bonding. In contrast, the salt of diprotonated 4,4'-biimidazolium showed a double linear chain mode of hydrogen-bonding to construct a three-dimensional network. The formation of two types of hydrogen-bonding modes made the difference in the stacking patterns of TCNQ columns and in their transport properties. The TCNQ salt of diprotonated 4,4'-biimidazolium exhibited high electrical conductivity (sigma(rt) = 1.1 x 10(-1) S cm(-1)). 相似文献
6.
[reaction: see text] The Peterson reaction between (t-BuO)Ph(2)SiCH(2)CN and various aldehydes furnishes the corresponding beta-monosubstituted alpha,beta-unsaturated cyanides with high Z selectivity (Z:E = 92:8 to >98:2). 相似文献
7.
Chatani N Amako K Tobisu M Asaumi T Fukumoto Y Murai S 《The Journal of organic chemistry》2003,68(4):1591-1593
The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction. 相似文献
8.
The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone. 相似文献
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