10.1002/anie.202009318
Angewandte Chemie International Edition
COMMUNICATION
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The molecular structure in the crystal in combination with the
failed reactions of the potassiated piperidide on its own and in
combination with potassium-t-butoxide with both styrene
derivatives show that the situation of the reactive potassium
amide is much more complex. Considerations are needed
whether parts of the structure observed in the crystal are also
involved in the reaction mechanism and influence the reaction
mechanism. Further anions such as the alkoxide anion seem to
be necessary in addition to the amide. Additionally, alkoxides
might also increase the solubility and by this increase the
reactivity. Also, two different or even more alkali metal ions must
be present. However, structure 10 represents only the
thermodynamic minimum of a decomposition product of THF and
does not show the desired reactivity.
In conclusion, highly reactive intermediates can be accessed
either by deprotonation reactions of phenethylamine derivates but
also by an alternative pathway: the addition of alkali metal amides
to the double bond. A stoichiometric aminometalation reaction of
styrene derivatives with potassium amides at low temperatures
without competing polymerization reactions is presented and the
possibility of quenching with different electrophiles is proven.
Quantum chemical calculations based on crystallized reactive
intermediates show a first insight into the reaction mechanism and
explain the advantage of potassiated amides in comparison to
lithiated amides in the aminometalation reactions. The isolation of
a complex potassium amide aggregate delivers first explanations
why a stoichiometric aminometalation works only with a mixture
of lithium, potassium, amide and alkoxide.
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Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (DFG) for
financial support. A. S. thanks the Studienstiftung des deutschen
Volkes for a fellowship. U. O. and L. B. thanks the Fonds der
Chemischen Industrie (FCI) for a Chemiefonds Fellowship. A. V.
thanks the Cusanuswerk for a fellowship.
Keywords: aminometalation • carbanions • alkali metals •
[14] E. Hevia, F. Mulks, L. Bole, L. Davin, A. Hernon-Gomez, A. R. Kennedy,
J. Gracia-Alvarez; doi.org/10.1002/anie.202008512
potassium • synergistic effects
[15] Reactions in deuterated THF or the use of stoichiometric amounts of
deuterated water did not result in a deuterated product. Traces of water,
such as hydroxides in tBuOK, may have a great influence on the reaction
and may serve as a proton source. For further Information see SI 2.3.2.4
p. 23.
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