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Volumn 43, Issue 12, 2010, Pages 5233-5237

Conducting thiophene-annulated azepine polymers

Author keywords

[No Author keywords available]

Indexed keywords

AMBIENT CONDITIONS; AZEPINES; ELECTROCHEMICAL POLYMERIZATION; MATERIALS RESEARCH; OXIDIZED STATE; REDOX PROPERTY; REDOX STABILITY; SEVEN-MEMBERED RINGS;

EID: 77953667186     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma100549w     Document Type: Article
Times cited : (14)

References (42)
  • 9
  • 30
    • 20544450502 scopus 로고    scopus 로고
    • Eds.;, 2 nd completely revised and enlarged edition; Wiley-VCH: Weinheim, Germany
    • de Meijere, A.; Diederich, F., Eds.; Metal-Catalyzed Cross-Coupling Reactions, 2 nd completely revised and enlarged edition; Wiley-VCH: Weinheim, Germany, 2003; Vol. 1.
    • (2003) Metal-Catalyzed Cross-Coupling Reactions , vol.1
    • De Meijere, A.1    Diederich, F.2
  • 31
    • 20544450502 scopus 로고    scopus 로고
    • Eds.;, 2 nd completely revised and enlarged edition; Wiley-VCH: Weinheim, Germany
    • de Meijere, A.; Diederich, F., Eds.; Metal-Catalyzed Cross-Coupling Reactions, 2 nd completely revised and enlarged edition; Wiley-VCH: Weinheim, Germany, 2003; Vol. 2.
    • (2003) Metal-Catalyzed Cross-Coupling Reactions , vol.2
    • De Meijere, A.1    Diederich, F.2
  • 36
    • 77951582979 scopus 로고    scopus 로고
    • DFT calculations also suggest that the one-electron oxidation of azepines (4 n - 1 state) gives rise to a slight expansion toward a planar conformation, the degree of which is smaller than that of two -electron oxidation (4 n - 2 state). This conformational change is probably due to the delocalization of the charge generated, not the aromatic stabilization, and seems to be true for most 4 n -electron conjugated cyclic systems, including thiepins and [8]annulenes. Similar geometric rearrangements are found to occur as well in simple N-functionalized 3-aminothiophenes. See
    • DFT calculations also suggest that the one-electron oxidation of azepines (4 n - 1 state) gives rise to a slight expansion toward a planar conformation, the degree of which is smaller than that of two -electron oxidation (4 n - 2 state). This conformational change is probably due to the delocalization of the charge generated, not the aromatic stabilization, and seems to be true for most 4 n -electron conjugated cyclic systems, including thiepins and [8]annulenes. Similar geometric rearrangements are found to occur as well in simple N-functionalized 3-aminothiophenes. See: Heth, C. L.; Tallman, D. E.; Rasmussen, S. C. J. Phys. Chem. B 2010, 114, 5275-5282
    • (2010) J. Phys. Chem. B , vol.114 , pp. 5275-5282
    • Heth, C.L.1    Tallman, D.E.2    Rasmussen, S.C.3
  • 40
    • 77953680146 scopus 로고    scopus 로고
    • 3P, and switching to the BINAP ligand furnished the desired N -benzylazepine 4d. However, the yield was low presumably due to reduced reactivity of the first amination product. It appears that while the bidentate ligands successfully suppress the undesired β-hydride elimination, the catalyst complex is not active enough for the cyclization step (the second amination)
    • 3P, and switching to the BINAP ligand furnished the desired N -benzylazepine 4d. However, the yield was low presumably due to reduced reactivity of the first amination product. It appears that while the bidentate ligands successfully suppress the undesired β-hydride elimination, the catalyst complex is not active enough for the cyclization step (the second amination).
  • 41
    • 77953660408 scopus 로고    scopus 로고
    • The oxidation potential of nitrogen-substituted thiophenes has been shown to be very sensitive to changes in nitrogen substitution. See ref 36
    • The oxidation potential of nitrogen-substituted thiophenes has been shown to be very sensitive to changes in nitrogen substitution. See ref 36.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.