Dissertation/Thesis Abstract

Enantioselective Mannich-type Reactions Promoted by Strained Silane Lewis Acids: Selective Generation of Two Contiguous Stereocenters and Entry into a Novel Class of Pyrrolidines
by Baxter, Jenny M., Ph.D., Columbia University, 2010, 250; 3447871
Abstract (Summary)

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.

Indexing (document details)
Advisor: Leighton, James L.
Commitee:
School: Columbia University
School Location: United States -- New York
Source: DAI-B 72/05, Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Organic chemistry
Keywords: Hydroamination, Mannich-type reactions, Pyrrolidines, Strained silanes
Publication Number: 3447871
ISBN: 978-1-124-53318-6
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