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Volumn 73, Issue 12, 2008, Pages 4721-4724

Iminyl radicals from α-azido o-iodoanilides via 1,5-H transfer reactions of aryl radicals: New transformation of α-azido acids to decarboxylated nitriles

Author keywords

[No Author keywords available]

Indexed keywords

ACIDS; ADDITION REACTIONS; CHEMICAL REACTIONS; CYANIDES; DIFFERENCE EQUATIONS; HYDROGEN; MATHEMATICAL TRANSFORMATIONS;

EID: 45249099757     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo800453z     Document Type: Article
Times cited : (51)

References (54)
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    • Selected examples:(a) Benati, L.; Montevecchi, P. C.; Spagnolo, P. Tetrahedron Lett. 1978, 815.
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    • Selected examples:(a) Kim, S.; Joe, G. H.; Do, J. Y. J. Am. Chem. Soc. 1993, 115, 3328.
    • Selected examples:(a) Kim, S.; Joe, G. H.; Do, J. Y. J. Am. Chem. Soc. 1993, 115, 3328.
  • 29
    • 0003168906 scopus 로고    scopus 로고
    • For reviews on aminyl radical cyclizations onto alkenes, see:a
    • For reviews on aminyl radical cyclizations onto alkenes, see:(a) Zard, S. Z. Synlett 1996, 1148.
    • (1996) Synlett , pp. 1148
    • Zard, S.Z.1
  • 41
    • 2442630750 scopus 로고    scopus 로고
    • 3SnH, see:(a) Beckwith, A. L. J.; Bowry, V. W.; Bowman, W. R.; Mann, E.; Parr, J.; Storey, J. M. D. Angew. Chem., Int. Ed. 2004, 43, 95.
    • 3SnH, see:(a) Beckwith, A. L. J.; Bowry, V. W.; Bowman, W. R.; Mann, E.; Parr, J.; Storey, J. M. D. Angew. Chem., Int. Ed. 2004, 43, 95.
  • 43
    • 45249088578 scopus 로고    scopus 로고
    • This mechanism apparently occurred to a minute extent also with iminyl radical 4e, as suggested by isolation of trace amounts of N-methyl-N-phenylcarbamoyl cyanide from the reaction of anilide 1e
    • This mechanism apparently occurred to a minute extent also with iminyl radical 4e, as suggested by isolation of trace amounts of N-methyl-N-phenylcarbamoyl cyanide from the reaction of anilide 1e.
  • 44
    • 0031570998 scopus 로고    scopus 로고
    • To the best of our knowledge no previous instances of α-(aminocarbonyl)iminyl radicals are available in the literature. The chemistry of other α-carbonyl-substituted analogues is virtually unknown, but recent chemical and/or spectral evidence would indicate that α-benzoyliminyl radical undergoes rapid fragmentation into benzoyl radical and a nitrile at temperatures exceeding-60°C, whereas the α-fluoroformyl counterpart is relatively stable, see:(a) Groenenboom, C. J.; Hageman, H. J.; Oosterhoff, P.; Overeem, T.; Verbeck, J. J. Photochem. Photobiol. A 1997, 107, 261.
    • To the best of our knowledge no previous instances of α-(aminocarbonyl)iminyl radicals are available in the literature. The chemistry of other α-carbonyl-substituted analogues is virtually unknown, but recent chemical and/or spectral evidence would indicate that α-benzoyliminyl radical undergoes rapid fragmentation into benzoyl radical and a nitrile at temperatures exceeding-60°C, whereas the α-fluoroformyl counterpart is relatively stable, see:(a) Groenenboom, C. J.; Hageman, H. J.; Oosterhoff, P.; Overeem, T.; Verbeck, J. J. Photochem. Photobiol. A 1997, 107, 261.
  • 46
    • 45249107803 scopus 로고    scopus 로고
    • In the case of iminyl 4f, alternative fragmentation at the alkyl side could be somewhat promoted by the notable stability of the released (3-indolyl)methyl radical
    • In the case of iminyl 4f, alternative fragmentation at the alkyl side could be somewhat promoted by the notable stability of the released (3-indolyl)methyl radical.
  • 47
    • 45249102481 scopus 로고    scopus 로고
    • The observed preference of iminyl radical 4 for β-fragmentation over intramolecular cyclization to oxoquinoxaline 7 was seemingly enhanced by the bulkyness of the adjacent R substituent (see Table 1).
    • The observed preference of iminyl radical 4 for β-fragmentation over intramolecular cyclization to oxoquinoxaline 7 was seemingly enhanced by the bulkyness of the adjacent R substituent (see Table 1).
  • 48
    • 0025324609 scopus 로고    scopus 로고
    • Selected examples:(a) Evans, D. A.; Britton, T. C.; Ellman, J. A.; Dorov, R. L. J. Am. Chem. Soc. 1990, 112, 4011.
    • Selected examples:(a) Evans, D. A.; Britton, T. C.; Ellman, J. A.; Dorov, R. L. J. Am. Chem. Soc. 1990, 112, 4011.
  • 53
    • 45249091044 scopus 로고    scopus 로고
    • Tin radicals were probably destroyed to a certain extent through H-abstraction reaction with those cyclohexadienyl radicals that arose from intramolecular addition of 10a onto the adjacent aromatic ring
    • Tin radicals were probably destroyed to a certain extent through H-abstraction reaction with those cyclohexadienyl radicals that arose from intramolecular addition of 10a onto the adjacent aromatic ring.
  • 54
    • 45249112379 scopus 로고    scopus 로고
    • Nitrile 12 was presumably the result of a β-hydrogen-atom abstraction mechanism operating on iminyl radical 10a.
    • Nitrile 12 was presumably the result of a β-hydrogen-atom abstraction mechanism operating on iminyl radical 10a.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.