Dienic δ-amino ketoesters, δ-amino ketones, and δ-amino esters have a trans-configuration of the protons at theγ, δ-double bond and exist predominantly in the S-trans-conformation. The dienic δ-amino ketones and δ-amino esters exist as the thermodynamically stable trans-isomers at theα, β-double bond, while the dienic δ-amino ketoesters represent equilibrium mixtures of the geometric isomers at the same double bond.
A rapid, on the NME time scale, rotation around theα,β-double bond under the equilibrium conditions was detected in the dienic δ-amino ketoesters. A hindering of the rotation around the C-N bond was noted in these compounds.
The kinetic reaction product of the addition of diethylamine to vinylacetylenic ketones and ketoesters is the cis-isomer at theα, β,-double bond, while the trans-isomer is formed as the result of subsequent isomerization. A scheme for the mechanism of these reactions was proposed.
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Zh. A. Krasnaya, T. S. Stytsenko, S. S. Yufim, E. P. Prokof'ev, and V. F. Kucherov, Izv. Akad. Nauk SSSR, Ser. Khim., 416 (1969).
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Prokof'ev, E.P., Krasnaya, Z.A. & Kucherov, V.F. Use of nmr method to study the stereochemistry of dienic δ-aminocarbonyl compounds. Russ Chem Bull 21, 2153–2159 (1972). https://doi.org/10.1007/BF00855287
- Double Bond
- Equilibrium Condition
- Kinetic Reaction