Reductive decomplexation of pi-allyltricarbonyliron lactone complexes using sodium naphthalenide as a route to stereodefined 1,7-diols and 2,3-diene-1,7-diols.
Treatment of pi-allyltricarbonyliron lactone complexes, that contain an adjacent leaving group, with lithium naphthalenide causes decomplexation to acyclic dienols in excellent yield and without any stereochemical scrambling of the allylic centre. When an endo complex is employed (E,E)-geometry prevails with good selectivity whereas (Z,E)-geometry dominates in the case of exo complexes. A mechanism consistent with the observed stereo- and regiochemistry is proposed.
Hollowood
Christopher J
CJ
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW.
Ley
Steven V
SV
D000438:Alcohols / Q000737:chemistry; D002254:Carbonates / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D007501:Iron / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D009281:Naphthalenes / Q000737:chemistry; D013237:Stereoisomerism
D000438:Alcohols; D002254:Carbonates; D007783:Lactones; D009281:Naphthalenes; C031721:naphthalene; D008094:Lithium; D007501:Iron