Fluoride Additive as a Simple Tool to Qualitatively Improve Performance of Nickel-Catalyzed Asymmetric Michael Addition of Malonates to Nitroolefins.

Oleg I Afanasyev, Fedor S Kliuev, Alexey A Tsygankov, Yulia V Nelyubina, Evgenii Gutsul, Valentin V Novikov, Denis Chusov

The Journal of organic chemistry 2022 Sep 16

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Nowadays, design of the new chiral ligands for organometallic catalysts is often based on the step-by-step increase in their complexity to improve efficiency. Herein we describe that simple in situ addition of the fluoride source to the asymmetric organometallic catalyst can improve not only activity but also enantioselectivity. Bromide-nickel diimine complexes were found to catalyze asymmetric Michael addition in low yields and ee, but activation with fluoride leads to a significant improvement in catalyst performance. The developed approach was applied to prepare several enantioenriched GABA analogues.

Citation

Oleg I Afanasyev, Fedor S Kliuev, Alexey A Tsygankov, Yulia V Nelyubina, Evgenii Gutsul, Valentin V Novikov, Denis Chusov. Fluoride Additive as a Simple Tool to Qualitatively Improve Performance of Nickel-Catalyzed Asymmetric Michael Addition of Malonates to Nitroolefins. The Journal of organic chemistry. 2022 Sep 16;87(18):12182-12195