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New Transformations from a 3-Silyloxy 2-Aza-1,3-diene: Consecutive Zr-Mediated Retro-Brook Rearrangement and Reactions with Electrophiles

✍ Scribed by Vincent Gandon; Philippe Bertus; Jan Szymoniak

Publisher: Elsevier Science
Year: 2000
Tongue: French
Weight: 118 KB
Volume: 56
Category: Article
ISSN: 0040-4020
DOI: 10.1016/s0040-4020(00)00310-0

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✦ Synopsis

AbstractÐA one-pot procedure for the transformation of the title compound to a-functionalized (silylated) and a,b-unsaturated secondary amides was described. The following steps were involved: a Zr-mediated retro-Brook rearrangement, selective deprotonation with n-BuLi on the organometallic intermediate, and trapping with electrophiles including alkyl and acyl halides and aldehydes. The electrophilic addition step occurred at a stabilized a-silyl carbanion center without affecting the near transition metal residue. In the case of aldehydes, the Peterson alkenation reaction took place on the transition metal complex in a highly stereoselective way.

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