1999
DOI: 10.1002/(sici)1099-0682(199907)1999:7<1111::aid-ejic1111>3.0.co;2-a
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Group-4 Metallocene Cation Complexes of Oligopeptides: Reaction of [Cp2ZrCH3(THF)+BPh4−] with Boc-Protected Di- and Tripeptide Esters

Abstract: The dipeptide derivatives Boc‐Gly‐Val‐OMe (2) and Boc‐Ala‐Val‐OMe (3) selectively add the methylzirconocene cation 1 to the carbonyl oxygen atom of the N‐terminal amino acid residue (ĸ‐C4=O coordination) upon treatment with [Cp2ZrCH3(THF)+BPh4−] in dichloromethane at low temperature (< 0 °C) to generate the complexes 2‐I and 3‐I, respectively. Above 0 °C methane is eliminated to give the stable chelate peptide metallocene cation complexes 2‐A and 3‐A, respectively, both featuring a combined C1=O/N2/C4=O coordi… Show more

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Cited by 19 publications

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“…A direct comparison between free MMA, which was present in stoichiometric excess in the solution at 253 K (see Figure ), revealed that the 1 H NMR resonances of the coordinated MMA are generally found at smaller δ values than the free MMA monomer [free/coordinated MMA: δ 6.00, 5.07/5.29, 5.04 (CH 2 ), δ 1.70/1.65 (CH 3 ), δ 3.26/3.11 (OCH 3 )]. The 13 C NMR carbonyl resonance of 19a appears at δ 178.4, which is shifted by Δδ = 8 ppm downfield from the corresponding value of the free MMA molecule in the solution (δ 170.5), which is typical for a strong group 4 metallocene cation coordination to a carbonyl functionality . Likewise, the same effect is observed for the 13 C NMR chemical shift of the MMA Michael position in 19a (δ 131.8) vs δ 126.2 (free MMA).…”
Section: The Search For Intermediatesmentioning
confidence: 61%
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.
“…A direct comparison between free MMA, which was present in stoichiometric excess in the solution at 253 K (see Figure ), revealed that the 1 H NMR resonances of the coordinated MMA are generally found at smaller δ values than the free MMA monomer [free/coordinated MMA: δ 6.00, 5.07/5.29, 5.04 (CH 2 ), δ 1.70/1.65 (CH 3 ), δ 3.26/3.11 (OCH 3 )]. The 13 C NMR carbonyl resonance of 19a appears at δ 178.4, which is shifted by Δδ = 8 ppm downfield from the corresponding value of the free MMA molecule in the solution (δ 170.5), which is typical for a strong group 4 metallocene cation coordination to a carbonyl functionality . Likewise, the same effect is observed for the 13 C NMR chemical shift of the MMA Michael position in 19a (δ 131.8) vs δ 126.2 (free MMA).…”
Section: The Search For Intermediatesmentioning
confidence: 61%
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.
“…This was expected as the less lipophilic salts are more readily precipitated from the solution by the addition of a less polar solvent. Similarly, the coupling between alanine and valine proceeded well under the same conditions when using 5a as the carbodiimide reagent (Table , entry 4) …”
Section: Resultsmentioning
confidence: 77%
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.
“…The terminal coordination of an ester group to a transition metal center can a priori take place through the carbonyl sp 2 oxygen atom or through the alkoxy sp 3 oxygen atom. In the majority of the cases (see ref for recent examples) the former coordination is obtained since it is favored both from a steric and also from an electronic viewpoint, the carbonyl group having the chance to form significant bonding through its π orbitals.
…”
Section: Resultsmentioning
confidence: 99%
“…Depc and dppc are pentadentate ligands that generally act as distorted tridentate meridional ligands through their N atom and through the two carbonyl O atoms from the ester group . These ligands can also be bonded to the metal center by the alkoxy O atoms, although it is a rare coordination mode. , The two different coordination modes are discussed in the present paper.…”
Section: Introductionmentioning
confidence: 88%
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.