1 Ocak 2011 Dergi makalesi Açık Erişim

Ucuncu, Muhammed; Karakus, Erman; Kus, Melih; Akpinar, Gurkan Eray; Aksin-Artok, Oezge; Krause, Norbert; Karaca, Sila; Elmaci, Nuran; Artok, Levent

Citation Style Language JSON

{
  "DOI": "10.1021/jo200201r", 
  "abstract": "Two methods involving the rhodium-catalyzed reaction of 2-en-4-yne acetates and the palladium-catalyzed reaction of 2-en-4-yne carbonates with organoboronic acids were investigated; both afforded exclusively the (E)-configured vinylallenes. The coordinative interaction of the rhodium with the acetate group promoted the delta-elimination of Rh(I)-OAc from the alkenylrhodium intermediate II in both syn and anti modes, with the syn-elimination being the major path. DFT calculations revealed that a conformer of this intermediate (II), which can lead to the (E)-configured vinylallene product via the syn-elimination mode, is energetically the most favorable conformer. The rhodium-catalyzed procedure is not applicable to reactions involving (E)-configured enyne acetates, because the geometry of the alkenylrhodium intermediate that is derived from the corresponding (E)-enyne acetate would not allow such coordinative interaction to occur, The palladium-catalyzed method, which proceeds through formation of the c-vinylallenylpalladium intermediate, B, is suitable for both the (E)- and (Z)-configured enyne carbonates and appears to have a wider scope for both organoboronic acids and enyne substrates. The palladium-catalyzed reaction of an enantiomerically enriched enyne carbonate proceeded with racemization.", 
  "author": [
    {
      "family": "Ucuncu", 
      "given": " Muhammed"
    }, 
    {
      "family": "Karakus", 
      "given": " Erman"
    }, 
    {
      "family": "Kus", 
      "given": " Melih"
    }, 
    {
      "family": "Akpinar", 
      "given": " Gurkan Eray"
    }, 
    {
      "family": "Aksin-Artok", 
      "given": " Oezge"
    }, 
    {
      "family": "Krause", 
      "given": " Norbert"
    }, 
    {
      "family": "Karaca", 
      "given": " Sila"
    }, 
    {
      "family": "Elmaci", 
      "given": " Nuran"
    }, 
    {
      "family": "Artok", 
      "given": " Levent"
    }
  ], 
  "container_title": "JOURNAL OF ORGANIC CHEMISTRY", 
  "id": "21447", 
  "issue": "15", 
  "issued": {
    "date-parts": [
      [
        2011, 
        1, 
        1
      ]
    ]
  }, 
  "page": "5959-5971", 
  "title": "Rhodium- and Palladium-Catalyzed 1,5-Substitution Reactions of 2-En-4-yne Acetates and Carbonates with Organoboronic Acids", 
  "type": "article-journal", 
  "volume": "76"
}