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101.
[reaction: see text] A catalytic asymmetric conjugate arylation of racemic 5-(trimethylsilyl)cyclohex-2-enone with arylboronic acids was catalyzed by 3 mol % chiral amidophosphane- or BINAP-Rh(I) in dioxane-water (10:1) to afford trans- and cis-3-aryl-5-(trimethylsilyl)cyclohexanones in high enantioselectivity. Dehydrosilylation of the product mixture with cupric chloride in DMF gave 5-arylcyclohex-2-enones with up to 93% ee in good yield. Enantiofacial selectivity with chiral phosphane-Rh(I) exceeds the trans-diastereoselectivity that is maintained in the achiral or racemic phosphane-Rh(I)-catalyzed conjugate arylation of 5-(trimethylsilyl)cyclohexenone. 相似文献
102.
Hiroshi Maruoka Motoyoshi Yamazaki Yukihiko Tomioka 《Journal of heterocyclic chemistry》2004,41(4):641-646
2‐Arnino‐4,5‐dihydro‐3‐thiophenecarbonitriles 1a‐c reacted with α,β‐unsaturated ketones (e.g. methyl vinyl ketone 2 and benzalacetone 3 ) in the presence of titanium(IV) chloride to give the corresponding Michael adducts 4a‐c and 5a‐c. Thermal treatment of compounds 4a‐c and 5a‐c with titanium(IV) chloride caused intramolecular cyclocondensation to yield the corresponding tetrahydrothieno[2,3‐b]pyridines 6a‐c and 7a‐c. Aromatization of 6a‐c and 7a‐c with potassium tert‐butoxide in refluxing tert‐butyl alcohol pro ceeded smoothly to afford the corresponding dihydrothieno[2,3‐b]pyridines 8a‐c and 9a‐c. 相似文献
103.
Ifuku S Kamitakahara H Takano T Tanaka F Nakatsubo F 《Organic & biomolecular chemistry》2004,2(3):402-407
Cellulose was reacted with a series of 4-alkoxytrityl chlorides (C(n)TCl, n: number of carbon atoms in a saturated alkyl chain) under homogeneous reaction conditions in LiCl-N,N-dimethyl acetoamide to give a series of 6-O-(4-alkoxytrityl)celluloses (C(n)TC) with a high degree of substitution (DS), from 0.94 to 0.99, and with high regioselectivity at the 6-O position. Solubility of the C(n)TC in nonpolar solvents depended on the alkyl chain length: as the alkyl chain lengthens, cellulose derivatives become more hydrophobic and are readily soluble in nonpolar solvents, but not in polar solvents. Acetates of the C(4)-C(18)TC (C(4)-C(18)TCAc) showed anisotropic structures over melting temperatures (T(m)) examined under a polarized optical microscope (POM). Over isotropization temperatures (T(i)), flow birefringence were detected for C(12)-C(18)TCAc. The T(m) and T(i) decreased linearly with an increasing number of carbon atoms in the alkyl substituent. Wide-angle X-ray scattering (WAXS) studies of C(n)TC indicated that the fully extended side chains were perpendicular to the polymer backbone and interdigitated. These C(n)TC with the improved solubility may be used as starting materials for further derivatization focused on the secondary hydroxyl groups at the C-2 and C-3 positions. 相似文献
104.
Michael T.H. Liu Najmul H. Chishiti Michal Tencer Hideo Tomioka Yasuji Izawa 《Tetrahedron》1984,40(5):887-892
The photochemical and thermal decomposition of 3-chloro-3-benzyldiazirine have been studied in different reaction conditions. The decomposition gives rise to benzylchlorocarbene which can rearrange to E and Z chlorostyrene and/or react with the environment. In the presence of acetic acid the main product is 1-chloro-2-phenylethyl acetate. Experiments with acetic acid-d4 showed that some of the chlorostyrene is formed from the carbocation; other experiments conducted with tetramethylethylene as a carbene trapping agent show that the carbene is formed even in the presence of acetic acid. 相似文献
105.
106.
Hideo Tomioka Tetsuya Watanabe Makoto Hattori Naoki Nomura Katsuyuki Hirai 《Journal of the American Chemical Society》2002,124(3):474-482
A series of polybrominated diphenylcarbenes (DPCs) are generated by irradiation of the corresponding precursor diazomethanes, and their reactivities are investigated by means of low-temperature spectroscopies as well as laser flash photolysis. Triplet bis(2,4,6-tribromophenyl)carbene was shown to decay by undergoing dimerization and to have a half-life of 1 s in a degassed benzene solution at room temperature, some 6 orders of magnitude longer-lived than the parent DPC. Anomalous effects of para substituents on the stability of the triplet are noted. Thus, while the replacement of a 4-bromine group with a methyl group resulted in a sharp decrease in the lifetime, introduction of a tert-butyl group resulted in a dramatic increase in the lifetime; triplet bis(2,6-dibromo-4-tert-butylphenyl)carbene was shown to have a half-life of 16 s in solution at room temperature. Attempts to increase the stability of these polybrominated DPCs by buttressing effects of a m-bromine group and by the synergetic effect of bromine and methyl groups are also described. 相似文献
107.
(2,4,6-Tribromophenyl)(4-tert-butyl-2,6-dimethylphenyl)diazomethane (1a) was shown to be stable enough to survive Sonogashira coupling reaction conditions at an elevated temperature and gave not only a para-monosubstituted product, (4-trimethylsilylethynyl-2,6-dibromophenyl)(4-tert-butyl-2,6-dimethylphenyl)diazomethane (1b), but also a disubstituted one, [2,4-bis(trimethylsilylethynyl)-6-bromophenyl](4-tert-butyl-2,6-dimethylphenyl)diazomethane (1c), and a trisubstituted product, [2,4,6-tris(trimethylsilylethynyl)phenyl](4-tert-butyl-2,6-dimethylphenyl)diazomethane (1d). Triplet diphenylcarbenes (DPCs) generated by photolysis of those ethynylated diphenyldiazomethanes were characterized by ESR and UV-vis spectroscopies at low temperature and laser flash photolysis techniques in solution at room temperature. Although ESR data indicated that ethynyl groups at the ortho positions are likely to stabilize triplet DPCs both sterically and electronically more effectively than o-bromine groups, kinetic studies suggested that the stability of triplet DPCs is not increased by o-ethynyl groups, as opposed to o-bromine groups. It is likely that triplet DPCs decay by interacting with the o-ethynyl groups. 相似文献
108.
109.
110.
Ultrafast melting of a charge-ordered state has been observed in the photo-irradiated colossal magnetoresistive compound Pr0.7Ca0.3MnO3. Pump-and-probe spectroscopy experiments reveal the formation of a conducting phase with typical features of an insulator–metal
transition (IMT) after less than 1 ps. This phase is metastable and can be maintained for about 1 μs unless it is stabilized
persistently into a pathlike metallic region by an electric field. Although laser-induced lattice heating may play a role
in the initial excitation, electronic correlations are the dominant effect which leads to the formation of the metallic state
upon the breakdown of the charge-ordered state.
Received: 26 January 2000 / Published online: 16 June 2000 相似文献