A versatile and efficient approach for the synthesis of chiral 1,3-nitroamines and 1,3-diamines via conjugate addition to new (S,E)-γ-aminated nitroalkenes derived from L-α-amino acids

Abstract

New chiral (S,E)-γ-N,N-dibenzylated nitroalkenes 2a–c were synthesized from natural L-(α)-amino acids in five steps with overall yields of 68–88%. The conjugate addition of hydride, methoxide, nitronate and azide nucleophiles to 2a–c led to the corresponding chiral 1,3-nitroamines in 74–90% yield. The conjugate addition of cyanide anion to 2a,b was followed by HNO2 elimination affording chiral aminated acrylonitriles (73–98%). On the other hand, the azide anion reacted with 2a, in acetonitrile, via a [3 + 2]-cycloaddition in which HNO2 was lost, providing the corresponding 1,2,3-triazole derivative. Direct reduction of 1,3-nitroamine derivatives 9a,b produced the corresponding 1,3-diamines in good yields.

Keywords

• amino alcohol
• amino aldehyde
• azide addition
• Baylis–Hillman reaction
• cyanide addition
• Michael addition