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Volumn 34, Issue 1, 1993, Pages 179-182

Allylic alcohols as substrates for the palladium(0)-catalyzed allylic substitution

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE;

EID: 0027466059     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)60088-6     Document Type: Article
Times cited : (62)

References (57)
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    • Expanding Industrial Applications of Palladium Catalysts
    • (1990) Synthesis , pp. 739
    • Tsuji1
  • 9
    • 0002228292 scopus 로고
    • Intramolekulare stöchiometrische (Li, Mg, Zn) und katalytische (Ni, Pd, Pt) Metallo-En-Reaktionen in der Organischen Synthese
    • (1989) Angewandte Chemie , vol.28 , pp. 39
    • Oppolzer1
  • 33
    • 84918715419 scopus 로고    scopus 로고
    • 7
  • 34
    • 84918709019 scopus 로고    scopus 로고
    • Only a handful of examples of the Pd-catalyzed reaction of allylic alcohols with nucleophiles have been described. These reactions occur under extreme conditions: thus Pd(0)-catalyzed reactions of 2-propen-1-ol, ({itE})-but-2-en-1-ol, and 1-buten-3-ol with stabilized C-nucleophiles (\gb-ketoesters) occurs in toluene at 100 \dgC over 4\2-96h.{su10} Since this substitution occurs in the absence of a base, a mechanism involving an activation of allylic hydroxyl by a Lewis or Br\/onsted acid may be suggested. Another formal allylic substitution of a tertiary allylic hydroxyl by amino group (N-nucleophile){su11} is catalayzed by (MeCN){in2}PdCl{in2} and proceeds {itvia} a different mechanism, involving a Pd(II)-initiated electrophilic addition across the double bond followed elimination of Pd(OH){in2}. The Pd(II)-catalyzed reaction of allylic alcohols with diethyl malonate{su12} may be attributed to the electrophilic activation of the hydroxy group.
  • 45
    • 84918739376 scopus 로고    scopus 로고
    • 16 Similarly, Pd-catalyzed arylation wit
  • 47
    • 84918725108 scopus 로고    scopus 로고
    • Starý, I., Kočovský, P., unpublished results.
  • 50
    • 84918723748 scopus 로고    scopus 로고
    • Less reactive substrates required up to 8 h
  • 51
    • 84918763855 scopus 로고    scopus 로고
    • Biphenyl and phenol have been identified by products in all reactions
  • 52
    • 84918730215 scopus 로고    scopus 로고
    • from 13, a bis-allylation product (6%) has also been detected.
  • 53
    • 84918729486 scopus 로고    scopus 로고
    • The starting material (18% and 21%, respectively) was recovered
  • 56
    • 84918718064 scopus 로고    scopus 로고
    • The starting alcohol does not racemize under the reaction conditions as revealed by optical rotation of the recovered (26%) 16.
  • 57
    • 84918717187 scopus 로고    scopus 로고
    • Reactions of i – iii turned out to be non-selective as well, producing mixtures of all possible isomers (58–74%).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.