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Volumn 76, Issue 9, 2011, Pages 3416-3437

Approaches to the synthesis of 2,3-dihaloanilines. Useful precursors of 4-functionalized-1 H-indoles

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC PRECURSORS; FUNCTIONALIZATIONS; FUNCTIONALIZED; IN-SITU; SMILES REARRANGEMENT; STARTING MATERIALS; SYNTHETIC ROUTES;

EID: 79955565747     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo200406f     Document Type: Article
Times cited : (42)

References (95)
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    • Mercuriation:; Tetrahedron Lett. 2001, 42, 983-985 Lithiation: Heterocycles 1993, 36, 29-32
    • Wipf, P.; Yokokawa, F. Tetrahedron Lett. 1998, 39, 2223-2226 Mercuriation: Brown, M. A.; Kerr, M. A. Tetrahedron Lett. 2001, 42, 983-985 Lithiation: Iwao, M. Heterocycles 1993, 36, 29-32
    • (1998) Tetrahedron Lett. , vol.39 , pp. 2223-2226
    • Wipf, P.1    Yokokawa, F.2    Brown, M.A.3    Kerr, M.A.4    Iwao, M.5
  • 21
    • 79955565492 scopus 로고    scopus 로고
    • note
    • Only 2,3-dichloroaniline is commercially available.
  • 29
    • 79955567774 scopus 로고    scopus 로고
    • note
    • Only 2,3-dichloronitrobenzene is commercially available. Other 2,3-dihalonitrobenzene derivatives have been prepared as intermediates in the multistep syntheses of some 2,3-dihaloanilines. See refs 11 and 12.
  • 36
    • 48249089353 scopus 로고    scopus 로고
    • For a recent review about synthetic applications of arynes, see
    • For a recent review about synthetic applications of arynes, see: Sanz, R. Org. Prep. Proced. Int. 2008, 40, 215-291
    • (2008) Org. Prep. Proced. Int. , vol.40 , pp. 215-291
    • Sanz, R.1
  • 38
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    • note
    • A ca. 1:1 mixture of 7 and 1b was obtained at 0 °C.
  • 39
    • 0342326176 scopus 로고
    • Over this temperature benzyne formation is expected if the corresponding dilithiated species 2b would be formed. See
    • Over this temperature benzyne formation is expected if the corresponding dilithiated species 2b would be formed. See: Reavill, D. R.; RichardsonSt., K. Synth. Commun. 1990, 20, 1423-1436
    • (1990) Synth. Commun. , vol.20 , pp. 1423-1436
    • Reavill, D.R.1    Richardsonst, K.2
  • 40
    • 79955555367 scopus 로고    scopus 로고
    • note
    • At 0 °C no starting material remained in the crude reaction mixture, probably due to ortho -lithiation and further benzyne generation that gives rise to an untreatable mixture.
  • 43
    • 79955570955 scopus 로고    scopus 로고
    • note
    • 2NH.
  • 44
    • 10044276358 scopus 로고
    • See refs 20 and 22. See also
    • See refs 20 and 22. See also: Fisher, L. E.; Caroon, J. M. Synth. Commun. 1989, 19, 233-237
    • (1989) Synth. Commun. , vol.19 , pp. 233-237
    • Fisher, L.E.1    Caroon, J.M.2
  • 45
    • 80755141140 scopus 로고
    • For related formation of 7-lithiobenzothiazole derivatives, see:; J. Org. Chem. 1996, 5130-5133
    • Takagishi, S.; Katsoulos, G.; Schlosser, M. Synlett 1992, 360-362 For related formation of 7-lithiobenzothiazole derivatives, see: Stanetty, P.; Krumpak, B. J. Org. Chem. 1996, 61, 5130-5133
    • (1992) Synlett , vol.61 , pp. 360-362
    • Takagishi, S.1    Katsoulos, G.2    Schlosser, M.3    Stanetty, P.4    Krumpak, B.5
  • 47
    • 79955555146 scopus 로고    scopus 로고
    • note
    • Compound 10 probably comes from t -BuLi addition to the expected 2- tert -butoxy-7-iodobenzoxazole. In the same way, formation of 11 could likely be due to subsequent elimination of t -BuOH from 10 under the reaction conditions.
  • 48
    • 0008947740 scopus 로고
    • 2-Bromo-3-nitrochlorobenzene has been prepared from 2-chloro-6- nitroaniline, which is obtained as the minor isomer (14% yield) in the chlorination reaction of o -nitroaniline. See: Liedholm, B. Acta Chem. Scand. 1969, 23, 3175-3186
    • (1969) Acta Chem. Scand. , vol.23 , pp. 3175-3186
    • Liedholm, B.1
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    • note
    • 2.
  • 68
    • 79955556477 scopus 로고    scopus 로고
    • note
    • Easily prepared by reaction of commercially available 2-bromo-2-methylpropanoyl bromide with aqueous ammonium hydroxide. See ref 35a.
  • 70
    • 79955566522 scopus 로고    scopus 로고
    • note
    • On the other hand, treatment of 18ba with NaOH in ethanol did not give rise to any hydrolyzed compound even after prolonged time.
  • 80
    • 0034679471 scopus 로고    scopus 로고
    • Treatment of 22ba or 22ca with KO t Bu in DMF gave rise to lower yields of the corresponding indoles 23 (ca. 30%). See
    • Treatment of 22ba or 22ca with KO t Bu in DMF gave rise to lower yields of the corresponding indoles 23 (ca. 30%). See: Rodriguez, A. L.; Koradin, C.; Dohle, W.; Knochel, P. Angew. Chem., Int. Ed. 2000, 39, 2488-2490
    • (2000) Angew. Chem., Int. Ed. , vol.39 , pp. 2488-2490
    • Rodriguez, A.L.1    Koradin, C.2    Dohle, W.3    Knochel, P.4
  • 81
    • 79955558889 scopus 로고    scopus 로고
    • note
    • Although we also tried the selective monoalkynylation of 18bc with 1-ethynylcyclohexene, the use of <2 equiv of the alkyne gave rise to a mixture of the possible isomers bearing one alkynyl moiety at both C-2 and C-3 positions, along with minor amounts of the starting material and 25c.


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