β,β'-Functionalized N,N-divinyl-N-trimethylsilyloxyamines via silylation of β-substituted aliphatic nitro compounds. The investigation of the mechanism of the process using selective trapping reagents

Article abstract of DOI:10.1016/S0040-4020(97)00831-4

Hitherto unknown N,N-divinyl-N-trimethylsilyloxyamines of the general formula |XC(R)=CH|₂NOSiMe₃ (X = CO₂Me, CN, 5-methyloxycarbonylisoxazolin-3-yl; R = H, Me, CH(Me)CO₂Me) were obtained with moderate to good yields by silylation of nitro compounds XCH(R)CH₂NO₂ with N,O-bis(trimethylsilyl)acetamide. The mechanism of this reaction was studied by the example of silylation of methyl-3-nitropropionate using selective trapping reagents. Trimethylsilyl ester of the starting aci-nitro compound and methyl 2-nitroso acrylate were intercepted as consecutive intermediates. Thus, the silylation of β-functionalized nitro compounds could be presented as a convenient route to practically unknown β-substituted nitroso-alkenes XC(R)=CHNO which behave as active 1,3-heterodienes towards ethyl vinyl ether used as trapping reagent.