The addition reaction of monomeric lithium enolate (Z)-1, derived from propiophenone, to propene oxide 2, was examined to clarify the exact geometry of the transition state (TS) involved in this type of reaction. The eight possible TSs and the corresponding pathways, four leading to syn γ-hydroxy ketone (γ-HK) 3 and four leading to anti γ-HK 4, were compared, using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d) theory level in vacuo and in the presence of the reaction solvent (toluene/hexane). In every case, the favored pathway involves a TS where the enolate CC and the epoxide C−C are in a gauche relationship and where the Li+ is stabilized by some C−C and C−H σ bonds of epoxide 2.
|Autori interni:||POMELLI, CHRISTIAN SILVIO|
BIANUCCI, ANNA MARIA PAOLA
|Autori:||C. S. POMELLI; BIANUCCI A; P. CROTTI; L. FAVERO|
|Titolo:||A DFT Investigation of the Addition Reaction of Monomeric Lithium Enolate Derived from Propiophenone to Propene Oxide: Examination of the Possible Transition Structures|
|Anno del prodotto:||2004|
|Digital Object Identifier (DOI):||10.1021/jo034587m|
|Appare nelle tipologie:||1.1 Articolo in rivista|