175019-62-2Relevant academic research and scientific papers
Synthesis, protonation, and electrophilic alkylation of CpW(CO)2[η3-2-(phenylethynyl)allyl]
Cheng, Chi-Yi,Hsieh, Chao-Hsieh,Lee, Gene-Hsian,Peng, Shie-Ming,Liu, Rai-Shung
, p. 1565 - 1571 (2008/10/08)
CpW(CO)2[η3-2-(phenylethynyl)allyl] (2) was prepared from the reaction between CpW-(CO)3Na and 2-methylene-4-phenyl-3-butyn-1-yl tosylate, followed by decarbonylation with Me3NO. Treatment of 2 with CF3SO3H in cold CDCl3 produced a mixture of [CpW(CO)2-(η4-1-(benzylidene)trimethylenemethane)]X (3a) and CpW(CO)2(η3-2-CH 2X-4-phenyl-2,3-butadien-1-yl) (3b) (X = CF3SO3), which were characterized with 1H and 13C NMR spectra. Treatment of this mixture (3a,b) with a variety of nucleophiles gave compounds of the type CpW(CO)2(η3-2-CH 2X-4-phenyl-2,3-butadien-1-yl) (X = OH (4a), OMe (4b), iBuNH (4c), Me (4d), Ph (4e), CCPh (4f), H (4g)). In the presence of Bu4NI, protonation of 4d-e with CF3-SO3H in cold CH2Cl2 produced CpW(CO)I[η4-(2-PhCH2-3-XCH2)vinylketene] (X = Me (6a), Ph (6b)), the structural identity of which was established from an X-ray diffraction study of the analogous complex CpW(CO)I[η4-(2-PhCH2-3-ICH2)vinylketene] (6c). Treatment of 2 with a mixture of acetaldehyde and BF3·Et2O in cold CH2Cl2, followed by reduction of NaBH3-CN gave CpW(CO)2(η 3-2-methyl-4-phenyl-5-methyl-2,4-pentadien-1-yl) (7), which was characterized by X-ray structural analysis.
