Beilstein J. Org. Chem.2018,14, 3018–3024, doi:10.3762/bjoc.14.281
carbonyladdition; shielded acrylonitrile; Introduction
A carbanionic fragment shows nucleofugal behavior on breaking its single-bond connection with a developing electrophilic center. Apart from deprotonation reactions or formation of a separated ion pair and other trivial examples, the (at least
fission may also be used to generate different metal derivatives of the nucleofugal anions as equilibrium components. Fluoride-catalyzed, metal-free desilylation admitted carbonyl addition but blocked the retro-addition.
Keywords: alkoxide fission; desilylation; fragmentation; retro-addition; reversible
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Graphical Abstract
Scheme 1:
The nucleofugal carbanion unit C escapes from the alkoxides A1M1 or A1M2 (M = metal), generating th...