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Volumn 132, Issue 32, 2010, Pages 11323-11328

Synthesis of complex allylic esters via C-H oxidation vs C-C Bond formation

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL CARBOXYLIC ACIDS; C-C BOND FORMATION; C-C BONDS; CATALYTIC SYNTHESIS; COUPLING REAGENTS; STRATEGIC ADVANTAGES; TERMINAL OLEFINS;

EID: 77955564047     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja104826g     Document Type: Article
Times cited : (95)

References (67)
  • 1
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    • General C-H oxidation, aminations, alkylations
    • General C-H oxidation, aminations, alkylations
  • 4
    • 32644440329 scopus 로고    scopus 로고
    • references therein
    • Dick, A. R. and Sanford, M. S. Tetrahedron 2006, 62, 2439 and references therein
    • (2006) Tetrahedron , vol.62 , pp. 2439
    • Dick, A.R.1    Sanford, M.S.2
  • 16
    • 77955581076 scopus 로고    scopus 로고
    • Pd-catalyzed allylic C-H oxidations
    • Pd-catalyzed allylic C-H oxidations
  • 27
    • 77955572095 scopus 로고    scopus 로고
    • Pd-catalyzed allylic C-H aminations
    • Pd-catalyzed allylic C-H aminations
  • 36
    • 13444287979 scopus 로고    scopus 로고
    • Streamlining synthesis via late-stage C-H oxidation: (a) For first explicit demonstration of this concept, see
    • Streamlining synthesis via late-stage C-H oxidation: (a) For first explicit demonstration of this concept, see: Fraunhoffer, K. J., Bachovchin, D. A., and White, M. C. Org. Lett. 2005, 7, 223
    • (2005) Org. Lett. , vol.7 , pp. 223
    • Fraunhoffer, K.J.1    Bachovchin, D.A.2    White, M.C.3
  • 39
    • 77955572224 scopus 로고    scopus 로고
    • For excellent reviews, see
    • For excellent reviews, see
  • 42
    • 77955562331 scopus 로고    scopus 로고
    • For some elegant examples of late stage C-H hydroxylation and amination, see
    • For some elegant examples of late stage C-H hydroxylation and amination, see
  • 45
    • 77955563057 scopus 로고    scopus 로고
    • Reference 1e, 1l.
    • Reference 1e, 1l.
  • 46
    • 0346116581 scopus 로고    scopus 로고
    • Wiley-VCH: Weinheim, and references therein.
    • Otera, J. Esterification; Wiley-VCH: Weinheim, 2003, and references therein.
    • (2003) Esterification
    • Otera, J.1
  • 49
    • 77955561406 scopus 로고    scopus 로고
    • 2 intermediate. However, we cannot exclude the possibility of an alternative, albeit unprecedented, mechanism involving anti-Markovnikov oxy-palladation followed by regioselective I-hydride elimination. (2a) Significantly, when using catalytic amounts of a bidentate bis-sulfoxide ligand, high branched regioselectivity for ester formation is observed. (2a, 2b) Mechanistic studies suggest this regio-outcome arises from inner sphere functionalization from an electronically dissymmetric φ-allylPd(BQ)carboxylate species. (2b, 2c, 4c)
    • 2 intermediate. However, we cannot exclude the possibility of an alternative, albeit unprecedented, mechanism involving anti-Markovnikov oxy-palladation followed by regioselective I-hydride elimination. (2a) Significantly, when using catalytic amounts of a bidentate bis-sulfoxide ligand, high branched regioselectivity for ester formation is observed. (2a, 2b) Mechanistic studies suggest this regio-outcome arises from inner sphere functionalization from an electronically dissymmetric φ-allylPd(BQ)carboxylate species. (2b, 2c, 4c)


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