Steven John Coote

Synthesis and C-alkylation of hindered aldehyde enamines.

A new reactivity mode of hindered lithium amides with terminal epoxides is described whereby aldehyde enamines are produced via a previously unrecognized reaction pathway. Some of these aldehyde enamines display unprecedented C-alkylation reactivity toward unactivated primary and secondary alkyl halides. For comparison, the reactivity of aldehyde enamines synthesized via a traditional condensation method was examined. C- rather than N-alkylation was the dominant reaction pathway found with a range of electrophiles, making this route to alpha-alkylated aldehydes more synthetically useful than previously reported.

Straightforward synthesis of α,β-epoxysilanes from terminal epoxides by lithium 2,2,6,6-tetramethylpiperidide-mediated deprotonation-in situ silylation

Lithiation-in situ silylation of simple terminal epoxides using lithium 2,2,6,6-tetramethylpiperidide in combination with trimethylsilyl chloride provides a direct and experimentally convenient process for the synthesis of trans-α,β-epoxysilanes.