226957-45-5Relevant academic research and scientific papers
Synthesis and hydrolysis of [alkenyl(alkoxy)carbene]manganese complexes: Evidence for a transient allylic intermediate on the way to α,β-unsaturated aldehydes
Mongin, Carole,Ortin, Yannick,Lugan, Noel,Mathieu, Rene
, p. 739 - 742 (1999)
A variety of alkenylcarbene complexes [Cp'(CO)2Mn= C(OEt)CH=CHR] (3) (Cp' = TiS-MeCsH4) was obtained in a straightforward manner upon aldol condensation of [Cp'(CO)2Mn=C(OEt)CH3] (1) with aromatic and α,β- unsaturated aldehydes RC(H)O (2). The reaction is totally stereoselective, giving (E)- or (all-E)-alkenylcarbenes only. The protonation of 3 at low temperature followed by reaction with water affords the α,β-unsaturated aldehyde complexes [Cp'(CO)2Mn(n2-RCH=CHCHO] (5), from which the aldehydes RC(H)=C(H)C(H)O (6) were displaced by acetonitrile. The intermediate aldehyde complexes are shown to result from the hydrolysis of a transient cationic π- allyl species [Cp'(CO)2Mn(n3-RCHCHC(OEt)H]+ ([4]+) formed upon protonation of 3.
