1-aminoallyl anions

Ahlbrecht51 reported on the deprotonation of tertiary enamines at C3 and that the resulting 1-aminoallyl anions were so highly nucleophilic that they yielded gamma (y) products with many electrophiles El (equation 24). 

Inagaki and coworkers46 predicted that the 2-aminoallyl anion resulting from an enamine would be more stable than the corresponding 1-aminoallyl anion on the basis of orbital phase continuity-discontinuity arguments. In support of their hypothesis, deprotonation of the enamine of 1-morpholinocyclohexen-l-ene with -BuLi-TMEDA took place at position 2 rather than at position 3 (equation 25). Their model is also supported by the results of Woodward and coworkers52 for 2-pyrrolidino-1,4-dihydro-naphthalene, which is also deprotonated at the a position. 

Keyword homoenolate, chiral, formal hydroxylation, 1-aminoallyl anions, silylation, alkylation... 

Further, enamines (38) or allylamines (39) are deprotonated to give ambident 1-aminoallyl anions which react with chlorotrimethylsilane with high regio-selectivity to yield the versatile silylated enamines (40) only, and which may be hydrolysed, or further deprotonated and subsequently alkylated to give enamines (41), which themselves may be isolated or hydrolysed without further purification (Scheme 54). Similarly, the silylated enamines (43) are derived from (42). Surprisingly, compounds (43) react with a variety of carbon electrophiles in the presence of TiCU to give products derived from substitution at the y-position (Scheme 55). A(,iV-Bis(silyl)enamines react with carbonyl compounds in the presence of fluoride ion to provide an interesting route to 2-aza-l,3-dienes, Enamine products also result from the rearran ment of thioimidates derived... 

Degl Innocenti and coworkers showed a similar migration that occurred in an iV-silylatcd aminoallyl anion (equation 188)448. 

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