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Alkyliron and Alkylcobalt Reagents, VII. - On the Substitution of the Halogen of Alkenyl Chlorides, Alkenyl Fluorides, and Alkynyl Halides by Reagents of the Type R4MLi2 (M = Fe, Co)
Kauffmann, Thomas,Saelker, Reiner,Voss, Karl-Uwe
, p. 1447 - 1452 (2007/10/02)
Me4FeLi2 and Me4CoLi2, which are favourable reagents for the substitution of Br in alkenyl bromides, also proved to be favourable for the substitution of the halogen in alkenyl chlorides (yields 68-99 percent; nearly complete retention of configuration in the case of Me4FeLi2), β-fluorostyrene (best yield 92 percent), and 1-fluoronaphthalene (best yield 47 percent).Me4FeLi2 differentiates between various alkenyl chlorides in 1:1 competition experiments better than Me4CoLi2 and is the optimal reagent for the substitution of halogen in 1-chloro-2-phenylethyne (12), 1-bromo-2-phenylethyne (13), and 1-chloro-3-phenoxypropyne (15) by methyl (yields 70, 46, and 80 percent, respectively).Substitution of the halogen in 12 by the n-butyl, n-octyl, and phenyl residue is better achieved by the catalytic systems RMgBr + 2.5 mol percent FeCl2 (R = nBu, nOct, Ph; yields 75, 63, and 96 percent, respectively) than by the reagents nBu4FeLi2, nBu4Fe(MgBr)2, nOct4Fe(MgBr)2, or Ph4Fe(MgBr)2 (yields 18-28 percent). Key Words: Iron, organo complexes / Cobalt, organo complexes
