Efficient highly enantioselective nitro-Mannich and Mannich-type reactions with hydrazones promoted by strained silanes are described. Nitro-Mannich reactions of aromatic benzoyl hydrazones and the TES enolates of nitroethane, nitropropane, and β-phenylnitroethane provide products in 57–88% yield, 4:1 to 6:1 dr, and 85–92% ee. The addition of silyl ketene imines to both aromatic and aliphatic benzoyl hydrazones provides α, α-disubstituted, β-amino carboxylic acid equivalents in 36–84% yield, 4:1 to >20:1 dr, and 83–97% ee. The homoallylic variants of this class serve as substrates for metal-free, diastereoselective hydroamination reactions to access highly substituted pyrrolidines.
|Advisor:||Leighton, James L.|
|School Location:||United States -- New York|
|Source:||DAI-B 72/05, Dissertation Abstracts International|
|Keywords:||Hydroamination, Mannich-type reactions, Pyrrolidines, Strained silanes|
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