1027096-77-0Relevant academic research and scientific papers
Reactivity of the triple ion and separated ion pair of tris(trimethylsilyl) methyllithium with aldehydes: A RINMR study
Jones, Amanda C.,Sanders, Aaron W.,Sikorski, William H.,Jansen, Kristin L.,Reich, Hans J.
, p. 6060 - 6061 (2008)
Low-temperature rapid-injection NMR (RINMR) experiments were performed on tris(trimethylsilyl)methyllithium. In THF/Me2O solutions, the separated ion (1S) reacted faster than can be measured at -130 °C with MeI and substituted benzaldehydes (k ≥ 2 s-1), whereas the contact ion (1C) dissociated to 1S before reacting. Unexpectedly, the triple ion reacted faster with electron-rich benzaldehydes relative to electron-deficient ones. The addition of HMPA had no effect on the rate of reaction of the triple ion with p-diethylaminobenzaldehyde, and the immediate product of the reaction was the HMPA-solvated separated ion 1S, with the Peterson product forming only slowly. Thus, the aldehyde is catalyzing the dissociation of the triple ion. HMPA greatly decelerated the reaction of 1S (-10), providing an estimate of the Lewis acid activating effect of a THF-solvated lithium cation in an organolithium addition to an aldehyde. Copyright
