Diastereoselective reductive nitro-Mannich reactions
James C Anderson1, Alexander J Blake, Paul J Koovits
1Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK. j.c.anderson@ucl.ac.uk
Abstract:
A range of nitroalkenes 1 and imines 3 derived from alkyl, aryl, and heteroaryl aldehydes underwent a tandem 1,4-hydride addition nitro-Mannich reaction to afford anti-rich β-nitroamines 4. The crude anti-β-nitroamines 4 could be converted to the corresponding anti-β-nitroacetamides 5 (33 examples) to allow purification in good yield from the parent nitroalkenes (60-87%), and with a high diastereomeric ratio (90:10 to mostly >95:5). A representative selection of anti-β-nitroacetamides 5 (five examples) were reduced to vicinal diamines 7 with zinc hydrochloride; concomitant acyl migration provided differentially protected vicinal diamines 7 in good yield (80-91%).
Related Concept Videos
Phase I Reactions: Reductive Reactions
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Nitrosation of Enols
Nitriles to Ketones: Grignard Reaction
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Nitriles to Amines: LiAlH4 Reduction
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Electrophilic Aromatic Substitution: Nitration of Benzene


