Reactivity of the Triple Ion and Separated Ion Pair of Tris(trimethylsilyl)methyllithium with Aldehydes: A RINMR Study

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...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2008-05, Vol.130 (19), p.6060-6061
Main Authors: Jones, Amanda C, Sanders, Aaron W, Sikorski, William H, Jansen, Kristin L, Reich, Hans J
Format: Article
Language:English
Subjects:
Aldehydes - chemistry
Hempa - chemistry
Magnetic Resonance Spectroscopy - methods
Organometallic Compounds - chemistry
Trimethylsilyl Compounds - chemistry
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Summary: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 (
ISSN:0002-7863
1520-5126
DOI:10.1021/ja8003528