title: Sakurai addition and ring annulation of allylsilanes with alpha, beta-unsaturated esters. Experimental results and ab initio theoretical predictions examining allylsilane reactivity
abstract: Trimethylallylsilane has been shown to add to methyl acrylate in good yield when catalyzed by TiCl(4) at room-temperature despite literature reporting to the contrary. Further, even with these small alkyl ligands on the metal, ring annulation occurs to a large extent, in addition to simple allylation (Sakurai addition). The kinetic product is the ((trimethylsilyl)methyl)cyclobutane derivative which can be isomerized to cyclopentanoid, the thermodynamic product, if left in the presence of the catalyst. Consistent with other literature in this area, increasing the size of the ligands on silicon increases both the rate of product formation and the proportion of ring annulation relative to allylation. To develop a predictive model for allylsilane reactivity, ab initio gas-phase calculations have been made on the parent allylsilane with different ligands on the metal and on the reaction between these allylsilanes and acrolein, acrylic acid, and methyl acrylate. Predictions indicate that as the length of n-alkyl ligands on silicon increase, so does the apparent ability of the Si-Calpha bond of the allylsilane to hyperconjugate with developing vacant p orbital on Cbeta as the allylsilane begins to attack an electrophile. This is corroborated by a gradually increasing HOMO in the ground-state allylsilane as the ligands are changed from methyl through to n-hexyl and an increasing Si-Calpha bond length and decreasing Si-Calpha-Cbeta bond angle in the protonated species. These results in the gas phase mirror the reactivity of these n-alkyl-substituted allylsilanes in experiment; i.e., as the length of the alkyl chain increases, reactivity increases significantly. Triisopropylallylsilane, a very reactive silane, appears to anomalous in charge distribution and geometrical features compared with other substituted allylsilane systems which is due, presumably, to steric effects. The calculations on the protonated species would indicate that almost no hyperconjugative stabilization can occur on the basis of the bond lengths and angles necessary to promote good orbital overlap between the Si-Calpha bond and the empty p orbital on Cbeta. However, the gas-phase reaction of the triisopropylallylsilane with acrolein and methyl acrylate led to comparatively low energy barriers of 13.1 and 24.5, respectively, which is consistent with its high experimental reactivity. Together, this computational analysis has produced a useful model for predicting allylsilane reactivity and some possible explanations for this reactivity.
authors.affiliation: Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario, Canada M3J 1P3, and Guelph-Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ontario, Canada.
authors.initials: MG
authors.lastname: Organ
authors.initials: V
authors.lastname: Dragan
authors.initials: M
authors.lastname: Miller
authors.initials: RD
authors.lastname: Froese
authors.initials: JD
authors.lastname: Goddard