J Am Chem Soc
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
Published: April 2022
Merging electrochemistry with asymmetric catalysis promises to provide an environmentally friendly and efficient strategy for the construction of nonracemic chiral molecules. However, in practice, significant challenges arise from the instability or incompatibility of the chiral catalysts under the electrochemical conditions at the interface of electrode and solution. Herein, we report a catalytic asymmetric indirect electrolysis employing the combination of a redox mediator and a chiral-at-rhodium Lewis acid, which achieves a previously elusive enantioselective nucleophilic αC(sp)H alkenylation of ketones. Specifically, 2-acyl imidazoles react with potassium alkenyl trifluoroborates in high yields (up to 94%) and with exceptional enantioselectivities (27 examples with ≥99% ee) without the need for any additional stoichiometric oxidants (overall 40 examples). The new indirect electrosynthesis can be scaled to gram quantities and was applied to the straightforward synthesis of intermediates of the natural product cryptophycin A and a cathepsin K inhibitor.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/jacs.2c01686 | DOI Listing |
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!
© LitMetric 2025. All rights reserved.