Concerning the mechanism of the Peterson olefination reaction

Stereoselective Peterson Olefinations from Bench‐Stable Reagents and N‐Phenyl Imines

“…Similar results were obtained with 7 a when using TBAF as an activator (entry 10). Only derivative 7 g containing an electron‐withdrawing group and the tris(trimethylsilyl)methane 9 showed moderate 80:20 E / Z selectivities (entries 10–13) 4d. 9 While the lack of stereocontrol is a major drawback, monitoring of the reaction by 1 H NMR spectroscopy in [D 8 ]THF revealed that hexamethyldisiloxane was the reaction byproduct, which as a low‐boiling solvent (98 °C) can be readily removed (Table 1, Supporting Information).…”

Acid-catalyzed reactions of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl)oxiran. A new synthesis of functional-group-substituted vinylsilanes

“…In these reactions both isomers (Z and E) have been formed. The formation of Z-alkene is most likely favored due to pronounced differences in eclipsing interactions between the two possible conformations for syn elimination [5,13]. However, in the presence of two bulky groups ÀSiMe 3 and ÀSAr approximately equal amounts of E and Z isomers are formed.…”

1,4-bis[2,2-bis(trimethylsilyl)ethenyl]benzene: Regioselective ring opening of its α,β-epoxybis(silane) with some nucleophiles

“…In the reaction of 1 with 3 mmol of MCPBA the epoxybis(silane) 2 was the sole product formed. It has been reported [14] that the reaction of epoxybis(silane) with LiAlH 4 gave the b-hydroxybis(silane) without any formation of vinylsilane by Peterson-type reaction. However, in the case of epoxybis(silane) 2, Peterson-type olefination was found to take place after or concurrently with the addition, to give the corresponding vinylsilane 4 stereoselectively (Scheme 2).…”

“…However, this is not the case for the direct addition/elimination sequences. For example, the condensation of (Me 3 Si) 2 CHLi with benzaldehyde gave a mixture of stereoisomers (E/Z = 1.4/1) [14].…”