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Volumn 10, Issue 9, 2008, Pages 1715-1718

Oxidative amination of cuprated pyrimidine and purine derivatives

Author keywords

[No Author keywords available]

Indexed keywords

6 ((3 CHLORO)ANILINO) 2 (ISOPROPYL 2 HYDROXYETHYLAMINO) 9 ISOPROPYLPURINE; 6-((3-CHLORO)ANILINO)-2-(ISOPROPYL-2-HYDROXYETHYLAMINO)-9-ISOPROPYLPURINE; ADENINE; COPPER; CUPRIC CHLORIDE; DRUG DERIVATIVE; PURINE DERIVATIVE; PYRIMIDINE DERIVATIVE; THYMINE; URACIL;

EID: 48849106615     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol800353s     Document Type: Article
Times cited : (54)

References (40)
  • 10
    • 0032563315 scopus 로고    scopus 로고
    • Gray, N. S.; Wodicka, L.; Thunnissen, A.-M.; W. H.; Norman, T. C.; Kwon, S.; Espinoza, F. H.; Morgan, D. O.; Barnes, G.; LeClerc, S.; Meijer, L.; Kim, S.-H.; Lockhart, D. J.; Schultz. P. G. Science 1998, 281, 533.
    • (a) Gray, N. S.; Wodicka, L.; Thunnissen, A.-M.; W. H.; Norman, T. C.; Kwon, S.; Espinoza, F. H.; Morgan, D. O.; Barnes, G.; LeClerc, S.; Meijer, L.; Kim, S.-H.; Lockhart, D. J.; Schultz. P. G. Science 1998, 281, 533.
  • 12
    • 34248146411 scopus 로고    scopus 로고
    • For recent contributions in organocopper chemistry, see: a
    • For recent contributions in organocopper chemistry, see: (a) Deutsch, C.; Lipshutz, B. H.; Krause, N. Angew. Chem., Int. Ed. 2007, 46, 1650.
    • (2007) Angew. Chem., Int. Ed , vol.46 , pp. 1650
    • Deutsch, C.1    Lipshutz, B.H.2    Krause, N.3
  • 13
    • 84906441311 scopus 로고    scopus 로고
    • Application of Copper, Silver and Gold in Preparative Organic Chemistry
    • Crabtree, R. H, Mingos, D. M. P, Eds, Elsevier: Oxford
    • (b) Krause, N.; Morita, N. Application of Copper, Silver and Gold in Preparative Organic Chemistry. In Comprehensive Organometallic Chemistry III; Crabtree, R. H., Mingos, D. M. P., Eds.; Elsevier: Oxford, 2007; Vol. 9, pp 501-586.
    • (2007) Comprehensive Organometallic Chemistry III , vol.9 , pp. 501-586
    • Krause, N.1    Morita, N.2
  • 23
    • 0000225263 scopus 로고    scopus 로고
    • The deprotonation at C5 position of 2,4-dimethoxypyrimidine was described using lithiated bases: (a) Wada, A; Yamamoto, J.; Kanatomo, S. Heterocycles 1987, 3, 585.
    • The deprotonation at C5 position of 2,4-dimethoxypyrimidine was described using lithiated bases: (a) Wada, A; Yamamoto, J.; Kanatomo, S. Heterocycles 1987, 3, 585.
  • 30
    • 18244410426 scopus 로고    scopus 로고
    • For a recent method of C8-arylamino substitution on purines, see: Bookser, B. C.; Matelich, M. C.; Ollis, K.; Ugarkar, B. G. J. Med. Chem. 2005, 48, 3389.
    • For a recent method of C8-arylamino substitution on purines, see: Bookser, B. C.; Matelich, M. C.; Ollis, K.; Ugarkar, B. G. J. Med. Chem. 2005, 48, 3389.
  • 38
    • 0033241273 scopus 로고    scopus 로고
    • For the preparation of 4j. see: Hocek, M.; Holv, A. Collect. Czech. Chem. Commun. 1999, 64, 229.
    • For the preparation of 4j. see: Hocek, M.; Holv, A. Collect. Czech. Chem. Commun. 1999, 64, 229.
  • 39
    • 58149185909 scopus 로고    scopus 로고
    • This compound was prepared from 2-chloro-6-iodo-9H-purine using the Mitsonobu reaction procedure described in the following reference: Toyota, N, Katagari, A, Kanebo, C Synth. Commun. 1993, 23, 1295
    • This compound was prepared from 2-chloro-6-iodo-9H-purine using the Mitsonobu reaction procedure described in the following reference: Toyota, N.; Katagari, A.; Kanebo, C Synth. Commun. 1993, 23, 1295.
  • 40
    • 58149198391 scopus 로고    scopus 로고
    • Typical Procedure. Synthesis of 4-(2,6-Dimethoxypyrimidin-4-yl) morpholine (7a, A dry and argon-flushed 50 mL flask, equipped with a magnetic stirrer and a septum, was charged with a solution of 2,4-dimethoxypyrimidine (4a; 280 mg, 2 mmol. 1 equiv) in dry THF (1 mL, After the mixture was cooled to -40°C, TMPMgCl•LiC1 (1.20 M in THF; 1.84 mL, 1.1 mmol) was added dropwise and stirred for 12 h at -40°C. The resulting Grignard reagent was then added dropwise to a solution of CuCl•2LiCl (1.0 M in THF; 2.4 mL, 2.4 mmol, 1.2 equiv) and bis[2-(N,N-dimethylamino)ethy1] ether (284 mg, 2.4 mmol, 1.2 equiv) at -50°C and was stirred for 45 min affording the corresponding copper reagent 5a. N-Lithium morpholide (6a; 4 mmol) was added dropwise and the mixture was further stirred for 1 h at -60°C. The reaction mixture was cooled to -78°C, then chloranil (590 mg, 2.4 mmol) in dry THF 14 mL, was slowly added over a period of 1 h. The r
    • 2, pentane/ether; 4:1) affording the aminated pyrimidine 7a (341 mg, 76%) as a gray solid (mp 93.9-95.7°C).


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