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

Vera Lúcia Patrocinio Pereira; André Luiz da Silva Moura; Daniel Pais Pires Vieira; Leandro Lara de Carvalho; Eliz Regina Bueno Torres; Jeronimo da Silva Costa

doi:10.3762/bjoc.9.95

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

Beilstein J Org Chem. 2013 Apr 30:9:832-7. doi: 10.3762/bjoc.9.95. Print 2013.

Authors

Vera Lúcia Patrocinio Pereira¹, André Luiz da Silva Moura, Daniel Pais Pires Vieira, Leandro Lara de Carvalho, Eliz Regina Bueno Torres, Jeronimo da Silva Costa

Affiliation

¹ Núcleo de Pesquisas de Produtos Naturais, Laboratório de Síntese Estereosseletiva de Substâncias Bioativas, Universidade Federal do Rio de Janeiro, 21941-902, Rio de Janeiro, Brazil.

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: Baylis–Hillman reaction; Michael addition; amino alcohol; amino aldehyde; azide addition; cyanide addition.