PubMed Health⌕ Search

Biomedical subjects

Kenji Itoh

Publications and source records attributed to Kenji Itoh.

At least 37 records · Page 2Linked to original sources
PubMed2004

Brain electric activity for active inhibition of auditory irrelevant information.

We applied high resolution event-related potentials (ERPs) to assess brain activities associated with inhibition of irrelevant information processing during auditory selective attention. Ten healthy subjects performed an auditory selective attention task. ERPs in response to standard stimuli delivered to the unattended ear (irrelevant stimuli) and those delivered to the attended ear (relevant stimuli) were evaluated using temporally sequential scalp current density (SCD) mappings. For the irrelevant stimuli, current sources were located in the mid-frontal regions at 140-220 ms post-stimuli, and these SCD values were significantly larger than those for the relevant stimuli. These results suggest that auditory selective attention process involves not only focusing attention on relevant information, but also inhibitory processing of irrelevant information mediated by the frontal cortex.

Adult↗
PubMed2004

Palladium(0)-catalyzed cyclization of electron-deficient enynes and enediynes.

In the presence of a Pd(0) precatalyst, Pd2(bq)2(nbe)2 or Pd2(dba)3, 1,6-enyne esters were heated in refluxing benzene to give cyclodimers as single regioisomers. On the other hand, the combination of the Pd(0) precatalyst and triphenyl phosphite gave rise to various cycloisomerization products depending on the substitution pattern of the enyne esters. Six-membered ring cycloisomerization products were predominantly obtained from enyne esters bearing methallyl or 2-phenyl-2-propenyl moieties, while other enyne esters afforded normal five-membered ring cycloisomerization products. Intramolecular [2 + 2 + 2] cyclocotrimerization of enediyne esters also proceeded in the presence of the Pd(0) precatalyst and triphenylphosphine to give fused cyclohexadienes.

Journal Article↗
PubMed2004

Synthesis of benzo-fused lactams and lactones via Ru(II)-catalyzed cycloaddition of amide- and ester-tethered alpha,omega-diynes with terminal alkynes: electronic directing effect of internal conjugated carbonyl group.

In the presence of a catalytic amount of Cp*RuCl(cod), 1,6- and 1,7-diynes connected by an amide or an ester tether underwent cycloaddition with terminal alkynes at room temperature to give rise to cycloadducts in 40-93% yields with 63 : 37-83 : 17 regioisomer ratios.

Journal Article↗
PubMed2004

Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling.

The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjected to Suzuki-Miyaura cross-coupling with aryliodides to afford highly substituted biaryls in 53-76% yields.

Journal Article↗
PubMed2004

Spatial attention in individuals with pervasive developmental disorders using the gap overlap task.

The present study examined spatial attention in individuals with pervasive developmental disorders (PDD) using the gap overlap task and analyzed the express saccade, which is defined by its extremely short reaction time, as a measure of the state of attention. Participants were required to move their eyes to the target stimulus appearing on the left or right side of a fixation point. In this task, participants had to disengage their attention from the central fixation point and shift it to the peripheral target stimulus. In the gap condition, the fixation point disappeared 200 ms before the target stimulus was presented, and in the overlap condition, the fixation point remained while the target stimulus was presented. Saccade latencies were not different between the groups. However, the express saccade was more frequent in the PDD group than in the normal group in the overlap condition. We conclude that individuals with PDD have deficiencies in attentional engagement. Moreover, our study suggests that analysis of the express saccade will be useful in further examinations of attentional processes in PDD.

Adult↗
PubMed2004

Rhodium complex-catalyzed cycloisomerization of allenenes: exo and endo cyclization depending on the auxiliary ligands.

In the presence of a catalytic amount of a rhodium(I) complex, allenenes undergo cycloisomerization reactions resulting in the selective formation of exo-alkylidenecarbocycles and heterocycles. In the catalytic system of rhodium complexes with triaryl phosphites, cyclic 1,4- or 1,5-dienes are formed in good to excellent yields in the formal exo-cyclization mode via the metallacycle intermediate having an exo-alkylidene moiety. In this cycloisomerization, (E)- and (Z)-allenenes are transformed stereospecifically to the corresponding cyclic (E)- and (Z)-1,4-dienes, respectively. On the other hand, the reactions under carbon monoxide atmosphere exclusively afford seven-membered-ring products through an endo-mode cyclization. The unusual cyclization involves an allylic C-H activation process. The allenene bearing a silicon substituent at the olefinic terminus incorporates carbon monoxide to give the corresponding [2+2+1] cycloaddition product. This result apparently indicates that the catalysis of the rhodium complex is explained in terms of the oxidative cyclization of an allenene to furnish the key exo-alkylidene metallacycle intermediate at the first stage of the catalysis.

Journal Article↗
PubMed2004

Ruthenium-catalyzed one-pot double allylation/cycloisomerization of 1,3-dicarbonyl compounds leading to exo-methylenecyclopentanes.

The ruthenium-catalyzed one-pot double allylation/cycloisomerization of 1,3-diketones and methyl acetoacetate gave exo-methylenecyclopentanes in moderate to good yields with high isomer selectivity. The double allylation step effectively proceeded in the presence of a Ru(II) precatalyst, [Cp*RuCl(cod)], in 1,2-dichloroethane at 90 degrees C. The subsequent cycloisomerization was carried out upon addition of triethylsilane as a hydride source without purification of a 1,6-diene intermediate. Detailed inspections of the reaction by (1)H NMR spectroscopy disclosed that triethylsilyl methyl ether plays an important role for the conversion of a ruthenium(IV) allyl complex formed in the double allylation step into a ruthenium(II) species required for the cycloisomerization.

Journal Article↗
PubMed2003

Ruthenium(II)-catalyzed selective intramolecular [2 + 2 + 2] alkyne cyclotrimerizations.

In the presence of a catalytic amount of Cp*RuCl(cod), 1,6-diynes chemoselectively reacted with monoalkynes at ambient temperature to afford the desired bicyclic benzene derivatives in good yields. A wide variety of diynes and monoynes containing functional groups such as ester, ketone, nitrile, amine, alcohol, sulfide, etc. can be used for the present ruthenium catalysis. The most significant advantage of this protocol is that the cycloaddition of unsymmetrical 1,6-diynes with one internal alkyne moiety regioselectively gave rise to meta-substituted products with excellent regioselectivity. Completely intramolecular alkyne cyclotrimerization was also accomplished using triyne substrates to obtain tricyclic aromatic compounds fused with 5-7-membered rings. A ruthenabicycle complex relevant to these cyclotrimerizations was synthesized from Cp*RuCl(cod) and a 1,6-diyne possessing phenyl terminal groups, and its structure was unambiguously determined by X-ray analysis. The intermediary of such a ruthenacycle intermediate was further confirmed by its reaction with acetylene, giving rise to the expected cycloadduct. The density functional study on the cyclotrimerization mechanism elucidated that the cyclotrimerization proceeds via oxidative cyclization, producing a ruthenacycle intermediate and subsequent alkyne insertion initiated by the formal [2 + 2] cycloaddition of the resultant ruthenacycle with an alkyne.

Journal Article↗
PubMed2003

Palladium(0)-catalyzed intramolecular [2+2+2] alkyne cyclotrimerizations with electron-deficient diynes and triynes.

In the presence of 2.5 mol % of [Pd(2)(dba)(3)] (dba=dibenzylideneacetone) and 5 mol % of PPh(3), nearly equimolar amounts of dimethyl nona-2,7-diyne-1,9-dioate derivatives (diyne diesters) and dialkyl acetylenedicarboxylates were allowed to react in toluene at 110 degrees C to afford [2+2+2] cycloadducts in moderate-to-good yields. Similarly, dimethyl trideca-2,7,12-triyne-1,13-dioate derivatives (triyne diesters) were catalytically transformed into phthalic acid ester analogues in excellent yields. To gain insight into the mechanism of these intramolecular alkyne cyclotrimerizations, stoichiometric reactions of [Pd(2)(dba)(3)] with a diyne diester and a triyne diester bearing ether tethers were conducted in acetone at room temperature to furnish an oligomeric bicyclopalladacyclopentadiene and a Pd(0) triyne complex, respectively. The structures of these novel complexes were unequivocally determined by Xray structure analysis. The isolated triyne complex was heated at 50 degrees C or treated with PPh(3) in acetone at room temperature to afford the arene product. Furthermore, the same complex catalyzed the triyne cyclization with or without PPh(3).

Journal Article↗
PubMed2003

Neuromagnetic correlates of impaired automatic categorical perception of speech sounds in schizophrenia.

Schizophrenia is associated with dysfunction in language processing. At the earliest stage of language processing, dysfunction of categorical perception of speech sounds in schizophrenia has been demonstrated in a behavioral task. The aim of this study was to assess automatic categorical perception of speech sounds as reflected by event-related changes in magnetic field power in schizophrenia. Using a whole-head magnetoencephalographic recording, the magnetic counterpart of mismatch negativity (MMNm) elicited by a phonetic change was evaluated in 16 right-handed patients with chronic schizophrenia and in 19 age-, sex-, and parental socioeconomic status-matched normal control subjects. Three types of MMNm (MMNm in response to a duration decrement of pure-tone stimuli; a vowel within-category change [duration decrement of Japanese vowel /a/]; vowel across-category change [Japanese vowel /a/ versus /o/]) were recorded. While the schizophrenia group showed an overall reduction in magnetic field power of MMNm, a trend was found toward more distinct abnormalities under the condition of vowel across-category change than under that of duration decrement of a vowel or tone. The patient group did not show abnormal asymmetries of MMNm power under any of the conditions. This study provides physiological evidence for impaired categorical perception of speech sounds in the bilateral auditory cortex in schizophrenia. The language-related dysfunction in schizophrenic patients may be present at the early stage of auditory processing of relatively simple stimuli such as phonemes, and not just at stages involving higher order semantic processes.

Adult↗
PubMed2002

Selective synthesis of fused cyclooctatetraenes by [4 + 4] coupling between two different diene units.

In the presence of CuCl and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, the [4 + 4] coupling between zirconacyclopentadienes and 1,3-diiodobutadienes fused through an oxygen or nitrogen five-membered ring proceeded at ambient temperature to afford fully substituted polycyclic cyclo-octatetraenes in good yields. The fused ring moiety of the diiodides plays a critical role. The corresponding acyclic diiodide and a cyclohexane-fused analogue gave no coupling product, and a cyclopentane derivative showed only moderate reactivity. Correlation of the structures of the diiodides and their reactivity was established by an X-ray and density functional study.

Journal Article↗
PubMed2002

Ir-Catalyzed substitution of propargylic-type esters with enoxysilanes.

Propargylic-type acetates react readily with enoxysilanes in the presence of 1 mol % of [Ir(cod){P(OPh)3}2]OTf activated preliminarily with molecular H2 to give beta-alkynyl ketones in high to excellent yields. Substitution at the propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.

Journal Article↗
PubMed2002

Ruthenium(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes with tricarbonyl compounds.

In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=O double bonds to selectively afford dienones via electrocyclic ring opening of the expected alpha-pyrans. The intramolecular Michael addition of the cycloadducts having an acetyl and an alkylidenemalonate moiety gave bicyclo[3.3.0]octenone derivatives.

Journal Article↗