Nucleofugal behavior of a β-shielded α-cyanovinyl carbanion

• Rudolf Knorr and
• Barbara Schmidt

Beilstein J. Org. Chem. 2018, 14, 3018–3024, doi:10.3762/bjoc.14.281

• 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

• formally) heterolytic cleavage of C–C single bonds can provide cases of interest if it generates organometallic compounds under unusual conditions. The well-known cases of alkoxide fission [1][2][3] (top line of Scheme 1) may be viewed as a reversed formation of an alkoxide A1M1 from an organometallic C–M1

• , metal cation assistance was not necessary for the rapid carbanion release from the α-silyl compound 24 in the presence of Bu4N+F− in catalytic amounts. (ii) Most of the above alkoxide fission reactions were conducted in the presence of an electrophile for trapping the released nucleofugal carbanion