Ethylenamine

The cationic BINAP-Rh complexes catalyze asymmetric 1,3-hydrogen shifts of certain alkenes. Diethylgeranylamine can be quantitatively isomerized in THF or acetone to citronellal di-ethylenamine in 96-99% ee (eq 17). This process is the key step in the industrial production of (-)-menthol. In the presence of a cationic (R)-BINAP-Rh complex, (5)-4-hydroxy-2-cyclopentenone is isomerized five times faster than the (R) enantiomer, giving a chiral intermediate of prostaglandin synthesis. ... 

Generation of the double bond of enamines is possible via a rDA reaction. Ethylenamine and its methyl derivatives have been prepared by FVP of the corresponding anthracene adducts (equation 24). Identification of the primary enamines in a pure state has been accomplished at -80 °C, while the less... 

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