1996
DOI: 10.1002/(sici)1099-1395(199608)9:8<529::aid-poc813>3.0.co;2-1
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Mechanistic aspects of aminium salt-catalyzed Diels-Alder reactions: The substrate ionization step

Abstract: Substituent effects in the aminium salt catalyzed Diels-Alder reactions of 2,3-dimethyl-l,3-butadiene with a series of metu and pam substituted /3-methylstyrenes are used to probe detailed mechanistic aspects of these reactions. Kinetic studies were carried out using two different aminium salt catalysts and also electrochemically, using anodic potentials corresponding to the oxidation potentials of the aminium salts. Substituent effects in the equilibrium oxidations of the styrene substrates to the correspondi… Show more

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Cited by 36 publications

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“…Cyclic voltammetry measurement showed that the oxidation potential of anethole was 1.17 eV vs SCE, which made its direct oxidation by the photogenerated hole of B-BT ( E oxi = 1.73 V vs SCE) possible . Based on the observations, we proposed a reaction mechanism similar to previous reports .…”
supporting
confidence: 79%
Exaggerated anticipatory anxiety is common in social anxiety disorder (SAD). Neuroimaging studies have revealed altered neural activity in response to social stimuli in SAD, but fewer studies have examined neural activity during anticipation of feared social stimuli in SAD. The current study examined the time course and magnitude of activity in threat processing brain regions during speech anticipation in socially anxious individuals and healthy controls (HC). Method Participants (SAD n = 58; HC n = 16) underwent functional magnetic resonance imaging (fMRI) during which they completed a 90s control anticipation task and 90s speech anticipation task.
“…Cyclic voltammetry measurement showed that the oxidation potential of anethole was 1.17 eV vs SCE, which made its direct oxidation by the photogenerated hole of B-BT ( E oxi = 1.73 V vs SCE) possible . Based on the observations, we proposed a reaction mechanism similar to previous reports .…”
supporting
confidence: 79%
Exaggerated anticipatory anxiety is common in social anxiety disorder (SAD). Neuroimaging studies have revealed altered neural activity in response to social stimuli in SAD, but fewer studies have examined neural activity during anticipation of feared social stimuli in SAD. The current study examined the time course and magnitude of activity in threat processing brain regions during speech anticipation in socially anxious individuals and healthy controls (HC). Method Participants (SAD n = 58; HC n = 16) underwent functional magnetic resonance imaging (fMRI) during which they completed a 90s control anticipation task and 90s speech anticipation task.
“…Early studies by Snider have shown a similar preference for 8- endo cyclization in acyclic acetoacetate systems 17,1e. While oxidative conditions have been used to promote formal [4+2] cycloadditions,18 to our knowledge this is the first example of a Mn(III)/Cu(II)-mediated [4+2] cycloaddition process. Moreover, the central bicyclo[2.2.2]octanone core is present in numerous bioactive natural products 19.…”
mentioning
confidence: 73%
Exaggerated anticipatory anxiety is common in social anxiety disorder (SAD). Neuroimaging studies have revealed altered neural activity in response to social stimuli in SAD, but fewer studies have examined neural activity during anticipation of feared social stimuli in SAD. The current study examined the time course and magnitude of activity in threat processing brain regions during speech anticipation in socially anxious individuals and healthy controls (HC). Method Participants (SAD n = 58; HC n = 16) underwent functional magnetic resonance imaging (fMRI) during which they completed a 90s control anticipation task and 90s speech anticipation task.
“…Analogous kinetic studies were also carried out in the more polar solvent acetonitrile (Table ). Again the plot of log k / k 0 vs σ (Figure , r 2 = 0.995) is far superior to that vs σ + (Figure , r 2 = 0.924), and the statistical significance of the distinction is borne out by F tests for the data in both solvents 2 Hammett−Brown plot for the Diels−Alder cycloadditions of aryl vinyl sulfides to 1,3-cyclopentadiene, catalyzed by 1 • + in dichloromethane at 0 °C (log k rel = −0.20 − 2.68σ + ; r 2 = 0.915).
3 Hammett plot for the Diels−Alder cycloadditions of aryl vinyl sulfides to 1,3-cyclopentadiene, catalyzed by 1 • + in acetonitrile at 0 °C (log k rel = 0.12 − 3.85σ; r 2 = 0.995).
4 Hammett−Brown plot for the Diels−Alder cycloadditions of aryl vinyl sulfides to 1,3-cyclopentadiene, catalyzed by 1 • + in acetonitrile at 0 °C (log k rel = −0.24 − 2.42σ + ; r 2 = 0.924).
1 Relative Rates of Diels−Alder Cycloadditions of Aryl Vinyl Sulfides to 1,3-Cyclopentadiene, Catalyzed by Tris(4-bromophenyl)aminium Hexachloroantimonate substituentlog k / k 0 (CH 2 Cl 2 )log k / k 0 (CH 3 CN) 4-MeO 1.36 1.210 4-Me 0.922 0.815 3-Me 0.450 0.327 H 0.000 0.000 4-Br −0.790 −0.652 3-Cl −1.480 −1.340 4-CF 3 −2.020 3,5-Cl 2 −1.95
…”
Section: Resultsmentioning
confidence: 94%
Exaggerated anticipatory anxiety is common in social anxiety disorder (SAD). Neuroimaging studies have revealed altered neural activity in response to social stimuli in SAD, but fewer studies have examined neural activity during anticipation of feared social stimuli in SAD. The current study examined the time course and magnitude of activity in threat processing brain regions during speech anticipation in socially anxious individuals and healthy controls (HC). Method Participants (SAD n = 58; HC n = 16) underwent functional magnetic resonance imaging (fMRI) during which they completed a 90s control anticipation task and 90s speech anticipation task.