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

Hitherto unknown N,N-divinyl-N-trimethylsilyloxyamines of the general formula [XC(R)=CH](2)NOSiMe3 (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 beta-functionalized nitro compounds could be presented as a convenient route to practically unknown beta-substituted nitroso-alkenes XC(R)=CHNO which behave as active 1,3-heterodienes towards ethyl vinyl ether used as trapping reagent. (C) 1997 Elsevier Science Ltd.