Base-Metal Catalysis - presented by Prof. Lingling Chu and Assoc. Prof. Ming Joo Koh and Prof. Zhan Lu and Assoc. Prof. Tatsuhiko Yoshino and Prof. Naohiko Yoshikai

Base-Metal Catalysis

Lingling Chu, Ming Joo Koh, Zhan Lu and Tatsuhiko Yoshino

Prof. Lingling ChuAssoc. Prof. Ming Joo KohAssoc. Prof. Tatsuhiko YoshinoProf. Zhan Lu
Slide at 28:15
Asymmetric Radical Multicomponent Couplings via Chelation Asymmetric carbo-alkenylation of alkenyl ketones Ni(cod)2 (10 mol%) C4F9 C4F9 (S,S)-L1 (12 mol%) Mn, PhCO2H DME, -30 °C (S,S)-sec-Bu-BiOx 85% yield, 90% ee N111 C4F9 C4F9 C4F9 R = OAc 86% yield, 92% ee 76% yield, 92% ee 88% yield, 90% ee = CO2Me 78% yield, 93% ee five-membered nickellacycles C4F9 C4F9 PhCO2H is critical 78% yield, 90% ee 75% yield, 92% ee ACS Catal. 2022, 12, 9779.
1
References
  • 1.
    F. Wang et al. (2022) Selective Three-Component Reductive Alkylalkenylation of Unbiased Alkenes via Carbonyl-Directed Nickel Catalysis. ACS Catalysis
Share slide
Summary (AI generated)

By using a specific strategy, we were able to achieve the first example of the carbon alkylation of β-γ unsaturated ketones. This was done by using LK highlights as coupling partners in the presence of Nickel cod and substituting with Ox Liki. This chemistry also demonstrates a good substrate scope and excellent initial selectivity control. The addition of benzoic acid was found to be important in enhancing efficiency. It is speculated that the nuclear cycles intermediate may be crucial in achieving high initial selectivity control for carbon alkylation.

Our second strategy involves a sensitization method using visible light to excite the planar ground state complex to its excited state.