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Volumn 127, Issue 50, 2005, Pages 17888-17893

Brønsted base-modulated regioselectivity in the aerobic oxidative amination of styrene catalyzed by palladium

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; ISOTOPES; MARKOV PROCESSES; PALLADIUM; STYRENE; THERMODYNAMICS;

EID: 29344454909     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0562806     Document Type: Article
Times cited : (111)

References (66)
  • 1
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    • For recent reviews and highlights, see: (a) Roundhill, D. M. Catal. Today 1997, 37, 155-165.
    • (1997) Catal. Today , vol.37 , pp. 155-165
    • Roundhill, D.M.1
  • 33
    • 1042276609 scopus 로고    scopus 로고
    • White and co-workers recently reported an example of Pd-catalyzed allylic oxidation of terminal alkenes that preferentially forms the branched or linear allylic acetate, depending on the reaction conditions: Chen, M. S.; White, M. C. J. Am. Chem. Soc. 2004, 126, 1346-1347.
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 1346-1347
    • Chen, M.S.1    White, M.C.2
  • 42
    • 29344438464 scopus 로고    scopus 로고
    • note
    • 2 complexes in the Cambridge Structural Database.
  • 43
    • 29344451501 scopus 로고    scopus 로고
    • note
    • 3] dependence correlates exclusively with [Pd] and not [Cu].
  • 44
    • 29344457672 scopus 로고    scopus 로고
    • note
    • 4OAc, a soluble source of acetate, achieves identical results at 10 mol % loading.
  • 45
    • 29344475524 scopus 로고    scopus 로고
    • note
    • See Supporting Information for additional details. The estimated uncertainty for individual rate measurements is ±10%.
  • 46
    • 29344442178 scopus 로고    scopus 로고
    • note
    • 3-benzylic intermediates arising from insertion of vinyl arenes into a Pd-H bond. Subsequent nucleophilic attack by an external amine results in formation of Markovnikov hydroamination products (see ref 6b).
  • 47
    • 29344456229 scopus 로고    scopus 로고
    • note
    • +) and the Pd(II)-hydride intermediate are utilized in the reduction of dioxygen to water.
  • 55
    • 29344435817 scopus 로고    scopus 로고
    • note
    • Rate law derivations are provided in the Supporting Information.
  • 56
    • 29344450472 scopus 로고    scopus 로고
    • note
    • 1H NMR spectroscopic studies to detect formation of such an intermediate have been inconclusive. The specific pathway for aminopalladation, however, does not alter our principle conclusion concerning the presence of a base-induced switch in regioselectivity.
  • 63
    • 0037149737 scopus 로고    scopus 로고
    • Recent mechanistic studies of platinum-catalyzed methods for the hydroamination of acrylonitrile and intramolecular hydroamination of alkenes indicate that exogenous amine serves as a Brønsted base to deprotonate the initially formed aminoplatination adduct: (a) Seul, J. M.; Park, S. J. Chem. Soc., Dalton Trans. 2002, 1153-1158.
    • (2002) Chem. Soc., Dalton Trans. , pp. 1153-1158
    • Seul, J.M.1    Park, S.J.2
  • 66
    • 29344464894 scopus 로고    scopus 로고
    • note
    • 3P)(alkene), possess a sterically encumbered triphenylphosphine ligand in the Pt(II) coordination sphere that may result in kinetically favored attack at the sterically less hindered alkene carbon.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.