3-Nitropropanoate ester

Twice deprotonated species from a 3-nitropropanoic ester is used in a double Michael reaction on 4,4-dimethoxy-2,5-cyclohexadienone to furnish bridged ring products (for a synthesis of gelsemine). The deprotonation is conveniently carried out with LDA in THF containing HMPA. ... 

Nitropropanoic acid esters can be converted into acrylic acid derivatives by treatment with a slight excess of DBU in THF or DMSO at room temperature. If 3-nitro-propanoates are treated with two equivalents of LDA at -78 °C in THF/DMPU or THF/HMPA, however, the resulting dianion can be cleanly C-alkylated, and the product isolated without elimination of the nitro group [160, 161] (Scheme 5.57). Without the addition of a cosolvent (DMPU, HMPA, or quinuclidine N-oxide [161]) alkylation of the 3-nitropropanoate dianion does not proceed sufficiently quickly [160,161],... 

Seebach, D. Henning, R. Mukhopadhyay, T. Doubly deprotonated methyl 3-nitropropano-ate, an acrylic ester d2-reagent. Chem. Ber. 

Figure 46 3-Nitropropanoic acid esters (193-195) from chrysomelid beetles and pinoresinol (35) from caterpillars of the cabbage butterfly, Pieris rapae.

Doubly deprotonated methyl 3-nitropropanoate is also useful for the synthesis of a-substituted acrylic esters. These compounds are prepared in good yield from substituted diethyl malonates by alkylation with 1-chloroethyl phenyl sulphide followed by dealkoxycarbOnylation. P-Substituted acrylic esters are readily prepared from the a-cyano-enamine (110) (Scheme 65). ... 

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