10.1002/chem.201701740
Chemistry - A European Journal
COMMUNICATION
Concluding, we presented a group of allylation reagents varying
their reactivity by introduction of remotely positioned residues.
Kinetic measurements with the conveniently accessible
boronates revealed fluorinated compound 2b to be the most
reactive in comparison to unsubstituted allylation reagent 2a
when treated with carbonyl compounds. Thus, for the first time,
reactivity could be enhanced to undergo conversion with ketones
yielding tertiary homoallylic alcohols. Only depending on the
allylation reagent’s configuration, all stereoisomers of the desired
products could be synthesised in excellent stereoselectivities and
good to very good yields. For 13 examples, it was demonstrated
how E and Z configured tertiary homoallylic alcohols can be
synthesised by a single, convenient method. Computational
investigations indicate that the enhanced reactivities is caused by
a ground-state destabilization of these fluorinated bisboronates.
Keywords: allylation • asymmetric catalysis • boron • quaternary
stereogenic center • computational chemistry
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Acknowledgements
The authors thank the Deutsche Forschungsgemeinschaft DFG,
the Fonds der Chemischen Industrie (Liebig-Scholarship to M.
Bre., Hoechst PhD scholarship to J.S.), the Heinrich-Heine-
Universität Düsseldorf, the Forschungszentrum Jülich GmbH, and
the University of Cologne within the excellence initiative for their
generous support of our projects. We are grateful to the Regional
Computing Center of the University of Cologne for providing
computing time of the DFG-funded High Performance Computing
(HPC) System CHEOPS as well as for their support.
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