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Volumn 9, Issue 7, 2007, Pages 1263-1266

Regio- and stereoselective lithiation and electrophilic substitution reactions of N-alkyl-2,3-diphenylaziridines: Solvent effect

Author keywords

[No Author keywords available]

Indexed keywords

AZIRIDINE DERIVATIVE; LITHIUM; ORGANOMETALLIC COMPOUND; SOLVENT;

EID: 34147175489     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0700714     Document Type: Article
Times cited : (42)

References (50)
  • 1
    • 0001318042 scopus 로고    scopus 로고
    • (a) Satoh, T. Chem. Rev. 1996, 96, 3303-3325.
    • (1996) Chem. Rev , vol.96 , pp. 3303-3325
    • Satoh, T.1
  • 3
    • 0242475011 scopus 로고    scopus 로고
    • For a special issue on oxiranyl and aziridinyl anions, see: Oxiranyl and Aziridinyl Anions as Reactive Intermediates in Synthetic Organic Chemistry, Tetrahedron Symposia-in-Print; Florio, S., Ed. Tetrahedron 2003, 59, 9693-9864.
    • (c) For a special issue on oxiranyl and aziridinyl anions, see: Oxiranyl and Aziridinyl Anions as Reactive Intermediates in Synthetic Organic Chemistry, Tetrahedron Symposia-in-Print; Florio, S., Ed. Tetrahedron 2003, 59, 9693-9864.
  • 6
    • 1542375289 scopus 로고    scopus 로고
    • (c) Hu, X. E. Tetrahedron 2004, 60, 2701-2743.
    • (2004) Tetrahedron , vol.60 , pp. 2701-2743
    • Hu, X.E.1
  • 30
    • 34147121134 scopus 로고    scopus 로고
    • The barrier for the nitrogen inversion is expected to be higher in the eis isomer, and only one isomer, indeed, is seen. It is worth pointing out that the two invertomers of cis-configured aziridines should have different energies since the one that put the alkyl group cis to the phenyl rings is the less stable one
    • The barrier for the nitrogen inversion is expected to be higher in the eis isomer, and only one isomer, indeed, is seen. It is worth pointing out that the two invertomers of cis-configured aziridines should have different energies since the one that put the alkyl group cis to the phenyl rings is the less stable one.
  • 34
    • 34147115615 scopus 로고    scopus 로고
    • 8 on aziridine trans-la, it was possible to study the nitrogen inversion. Aziridine trans1a showed only one signal for the aziridine protons at 293 K; cooling down the sample to 195 K, a splitting into two lines for the above protons is observed testifying a slow nitrogen inversion. The reduced rate of inversion with respect to the NMR time scale makes the two aziridine protons diastereotopic and then distinguishable. No splitting was observed in the case of the corresponding cis-aziridine ring protons.
    • 8 on aziridine trans-la, it was possible to study the nitrogen inversion. Aziridine trans1a showed only one signal for the aziridine protons at 293 K; cooling down the sample to 195 K, a splitting into two lines for the above protons is observed testifying a slow nitrogen inversion. The reduced rate of inversion with respect to the NMR time scale makes the two aziridine protons diastereotopic and then distinguishable. No splitting was observed in the case of the corresponding cis-aziridine ring protons.
  • 36
    • 3242659209 scopus 로고    scopus 로고
    • A complex-induced proximity effect could be operative in the α-lithiation of aziridines trans-1a-d; see: Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem., Int. Ed. 2004, 43, 2206-2225.
    • A complex-induced proximity effect could be operative in the α-lithiation of aziridines trans-1a-d; see: Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem., Int. Ed. 2004, 43, 2206-2225.
  • 37
    • 84986676623 scopus 로고    scopus 로고
    • Some spectroscopical evidences from an NMR investigation on these lithiated intermediates are in agreement with this hypothesis and results will be reported in due course; see also: Hoffmann, R. W.; Ruhl, T.; Chemla, F.; Zahneisen, T. Liebigs Ann. Chem. 1992, 719-724.
    • Some spectroscopical evidences from an NMR investigation on these lithiated intermediates are in agreement with this hypothesis and results will be reported in due course; see also: Hoffmann, R. W.; Ruhl, T.; Chemla, F.; Zahneisen, T. Liebigs Ann. Chem. 1992, 719-724.
  • 42
    • 34147168682 scopus 로고    scopus 로고
    • Moreover, we cannot rule out that an equilibrium between two isomeric lithiated intermediates could be present and that this could be differently shifted depending on the solvent
    • Moreover, we cannot rule out that an equilibrium between two isomeric lithiated intermediates could be present and that this could be differently shifted depending on the solvent.
  • 43
    • 34147112823 scopus 로고    scopus 로고
    • Relative stereochemistry has been ascertained by NOESY 2D and ID experiments; see the Supporting Information for details.
    • Relative stereochemistry has been ascertained by NOESY 2D and ID experiments; see the Supporting Information for details.
  • 45
    • 18844414256 scopus 로고    scopus 로고
    • For a recent report on the reactivity of α-amino-organolithiums, which are related to a-lithiated aziridines, see:, Rappoport, Z, Marek, I, Eds, Wiley & Sons: New York
    • For a recent report on the reactivity of α-amino-organolithiums, which are related to a-lithiated aziridines, see: Gawley, R. E.; Coldham, I. In The Chemistry of Organolithium Compounds, Part 2; Rappoport, Z., Marek, I., Eds.; Wiley & Sons: New York, 2004; pp 997-1052.
    • (2004) The Chemistry of Organolithium Compounds, Part 2 , pp. 997-1052
    • Gawley, R.E.1    Coldham, I.2
  • 46
    • 0034639903 scopus 로고    scopus 로고
    • In an attempt to demonstrate the intervening of a SET mechanism, bromomethylcyclopropane and 6-bromo-1-hexene were used as radical scavengers (see: (a) Gawley, R. E, Low, E, Zhang, Q, Harris, R. J. Am. Chem. Soc. 2000, 122, 3344-3350
    • In an attempt to demonstrate the intervening of a SET mechanism, bromomethylcyclopropane and 6-bromo-1-hexene were used as radical scavengers (see: (a) Gawley, R. E.; Low, E.; Zhang, Q.; Harris, R. J. Am. Chem. Soc. 2000, 122, 3344-3350.
  • 47
    • 33750973052 scopus 로고    scopus 로고
    • Gawley, R. E.; Eddings, D. B.; Santiago, M.; Vicic, D. A. Org. Biomol. Chem. 2006, 4, 4285-4291 in the trapping reaction of trans-1a-Li in toluene and hexane as the solvents. A complex reaction mixture was obtained in both cases. Only a small amount of the desired alkylated products was observed from a GC-MS analysis.
    • (b) Gawley, R. E.; Eddings, D. B.; Santiago, M.; Vicic, D. A. Org. Biomol. Chem. 2006, 4, 4285-4291) in the trapping reaction of trans-1a-Li in toluene and hexane as the solvents. A complex reaction mixture was obtained in both cases. Only a small amount of the desired alkylated products was observed from a GC-MS analysis.
  • 48
    • 34147096415 scopus 로고    scopus 로고
    • Kadaba, P. K.; Dahlman, D. L. U.S. Patent No. 4,582,827, 1986; Chem. Abstr. 1986, 105, 56366.
    • (a) Kadaba, P. K.; Dahlman, D. L. U.S. Patent No. 4,582,827, 1986; Chem. Abstr. 1986, 105, 56366.
  • 49
    • 34147157780 scopus 로고    scopus 로고
    • Chang, W.-H.; Piccirilli, R. U.S. Patent No. 4,528,333, 1985; Chem. Abstr. 1985, 103, 105744.
    • (b) Chang, W.-H.; Piccirilli, R. U.S. Patent No. 4,528,333, 1985; Chem. Abstr. 1985, 103, 105744.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.