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Volumn 131, Issue 43, 2009, Pages 15598-15599

Umpolung amination: Nickel-catalyzed coupling reactions of N,N-dialkyl-N-chloroamines with diorganozinc reagents

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; CHLOROAMINES; DIORGANOZINC REAGENTS; NICKEL CATALYZED COUPLING; ONE-POT PROCEDURES; ORGANOZINC REAGENTS; REACTION CONDITIONS; UMPOLUNG;

EID: 70350662869     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja907038b     Document Type: Article
Times cited : (155)

References (37)
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    • For Cu-catalyzed amination using hydroxylamines, see: (a) Berman, A. M.; Johnson, J. S. J. Am. Chem. Soc. 2004, 126, 5680.
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 5680
    • Berman, A.M.1    Johnson, J.S.2
  • 18
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    • For Ni-catalyzed amination using hydroxylamines, see
    • For Ni-catalyzed amination using hydroxylamines, see: Berman, A. M.; Johnson, J. S. Synlett 2005, 1799.
    • (2005) Synlett , pp. 1799
    • Berman, A.M.1    Johnson, J.S.2
  • 20
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    • N-Arylsuccinimide has been observed as a minor byproduct (8% yield) in NCS-mediated, Pd-catalyzed oxidative functionalization of C-H bonds. See
    • N-Arylsuccinimide has been observed as a minor byproduct (8% yield) in NCS-mediated, Pd-catalyzed oxidative functionalization of C-H bonds. See: Whitfield, S. R.; Sanford, M. S. J. Am. Chem. Soc. 2007, 129, 15142.
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 15142
    • Whitfield, S.R.1    Sanford, M.S.2
  • 22
    • 0001598172 scopus 로고
    • Our working hypothesis was based on a cross-coupling mechanism for the transformation that would be initiated by oxidative addition of the Ni catalyst into the N-Cl bond by a single-electron-transfer (SET) mechanism. For studies of oxidative addition of alkyl halides by an SET mechanism, see
    • Our working hypothesis was based on a cross-coupling mechanism for the transformation that would be initiated by oxidative addition of the Ni catalyst into the N-Cl bond by a single-electron-transfer (SET) mechanism. For studies of oxidative addition of alkyl halides by an SET mechanism, see: (a) Stille, J. K.; Cowell, A. B. J. Organomet. Chem. 1977, 124, 253.
    • (1977) J. Organomet. Chem. , vol.124 , pp. 253
    • Stille, J.K.1    Cowell, A.B.2
  • 25
    • 0001038041 scopus 로고
    • For reductive elimination of Ni amido complexes, see
    • For reductive elimination of Ni amido complexes, see: (d) Koo, K.; Hillhouse, G. L. Organometallics 1995, 14, 4421.
    • (1995) Organometallics , vol.14 , pp. 4421
    • Koo, K.1    Hillhouse, G.L.2
  • 26
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    • note
    • N2 attack of an arylnickel complex on the N-chloroamine (see ref 3d).
  • 27
    • 70350661234 scopus 로고    scopus 로고
    • note
    • DMA appears to play a key role in the reaction.
  • 28
    • 70350623662 scopus 로고    scopus 로고
    • note
    • See the Supporting Information for details of the ligand screen.
  • 29
    • 0008854673 scopus 로고
    • N-Chloroamines are known to oxidize phosphines. See
    • N-Chloroamines are known to oxidize phosphines. See: Sopchik, A. E.; Bentrude, W. G. Tetrahedron Lett. 1980, 21, 4679.
    • (1980) Tetrahedron Lett. , vol.21 , pp. 4679
    • Sopchik, A.E.1    Bentrude, W.G.2
  • 30
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    • note
    • In the absence of Ni(cod)2 and/or bipyridine, reaction of 1a with diphenylzinc under the standard reaction conditions afforded <5% yield of 3a.
  • 31
    • 70350667046 scopus 로고    scopus 로고
    • note
    • 1H NMR spectroscopy of the unpurified reaction mixture revealed that benzaldehyde was formed in 23% yield in this reaction. Its formation is tentatively attributed to β-hydride elimination from a Ni amido complex to form N-methylbenzaldimine, which was hydrolyzed upon aqueous workup.
  • 32
    • 0347694968 scopus 로고    scopus 로고
    • Electron-withdrawing substituents on N substantially slow the reductive elimination from arylpalladium amido complexes. See
    • Electron-withdrawing substituents on N substantially slow the reductive elimination from arylpalladium amido complexes. See: Yamashita, M.; Cuevas Vicario, J. V.; Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 16347.
    • (2003) J. Am. Chem. Soc. , vol.125 , pp. 16347
    • Yamashita, M.1    Cuevas Vicario, J.V.2    Hartwig, J.F.3
  • 36
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    • note
    • Cyclization of these substrates frequently proceeds by a radical mechanism (see ref 16c).
  • 37
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    • note
    • Preparation of 1j takes advantage of the chemoselectivity of the N-chlorination reaction toward the more nucleophilic nitrogen.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.