A Simple and Highly Diastereoselective One-Pot Synthesis of 1,3-Diamines

Asymmetric Mannich‐Type Reaction of a Chiral N‐(tert‐Butylsulfinyl) Ketimine with Imines: Application to the Synthesis of Chiral 1,3‐Diamines

“…The addition of lithium enolates to β-amino imines 3 provided the 1,1,3-trisubstituted 1,3-diamines 8 in good yields ( Table 5). As shown in Table 5, the reactions of β-amino imines 3, except 4-chlorophenyl-and furyl-β-amino imines (3b and 3h) (Entries 2 and 7), with ethyl acetate/LDA exhibited high diastereoselectivities (99:1 dr) without using any additives such as ClTi(OiPr) 3 . [16] The results of the nucleophilic addition of Grignard reagents to β-amino imines 3 are shown in Table 6.…”

“…In Kobayashi's work, chiral β-amino imines could be reduced by LiAl-H(OtBu) 3 in the presence of LiI to generate the optically active 1,3-diamine in good diastereoselectivity (syn/anti = 14:86).…”

“…Risch developed a synthetic method to 1,3-diamines by means of the aminoalkylation of enamines or imines with tertiary iminium salts, [2] followed by the reduction of the C=N double bond. [3] Nevertheless, there were few efficient methods available to synthesize optically active β-amino imines [3d,4] and 1,3-diamines [3d] until very recently.…”

Double‐Addition Reaction of Aryl Methyl Sulfones with N‐tert‐Butylsulfinyl Imines: Diastereoselective and Concise Synthesis of 2‐Sulfonylated 1,3‐Diamines

“…This method provides concise access to 2-sulfonylated 1,3-anti diamines with good to excellent diastereoselectivities. A number of synthetic methods, which are primarily based on the reduction of suitable precursors, including diimines, [3] 1,3-dinitro compounds, [4] pyrazolidines, [5] pyrimidines, [6] azides, [1d, 7] b-aminoimines, [8] and quaternary immonium salts, [9] have been reported. [1] Prominent examples include the HIV-protease inhibitor A-74704, [1a-b] natural tetraponerines, [1c-e] and the marine alkaloids batzelladines.…”

“…[1] Prominent examples include the HIV-protease inhibitor A-74704, [1a-b] natural tetraponerines, [1c-e] and the marine alkaloids batzelladines. A number of synthetic methods, which are primarily based on the reduction of suitable precursors, including diimines, [3] 1,3-dinitro compounds, [4] pyrazolidines, [5] pyrimidines, [6] azides, [1d, 7] b-aminoimines, [8] and quaternary immonium salts, [9] have been reported. [2] In this context, great efforts have been made to develop efficient protocols for the synthesis of 1,3-diamines.…”