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 1:33:16
Enantioselective CMD
metal
carboxylate
enantiotopic
C-H bonds
CMD mechanism:
chiral carboxylate assisted?
cf. Pd/MPAA
monodentate
flexible
bidentate ligand
Pd catalysis: Yu, J.-Q.; Houk, K. N. et al. Acc. Chem. Res. 2017, 50, 2853
1
References
  • 1.
    Y. Yang et al. (2017) Experimental–Computational Synergy for Selective Pd(II)-Catalyzed C–H Activation of Aryl and Alkyl Groups. Accounts of Chemical Research
Share slide
Summary (AI generated)

Chiral carboxylic acid or a chiral carboxylate is used for angio C one to collate. During activation, CP symmetric catalysis ch one to cleavage proceeds via a constructed meter. The proton mechanism, known as the cmed mechanism, involves the coordinating carboxylic acid working as a base to remove the proton without changing the oxidation state of the metal center, resulting in a metal cycle intermediate.

By introducing a chiral carboxylic acid, enantio ch mode cleavage can be achieved. The determining step in this process is ch mode activation. This strategy has been successfully utilized in para chemistry, where Professor Jin has used various groups to achieve excellent reactions based on this approach in selective ccied mechanism.

In paradigm chemistry, a BNT anionic ligand is used because a paradigm has full coordination sites. However, for CP symmetric catalysis, the complex only has three available coordination sites, with two already used for substrate carboxylic carboxy. An ion can only coordinate in a monodentate fashion to the metal, making the conformation very flexible and ruling out the use of a bidentate Riggan.

Therefore, a specific design for the chiral carboxylic acid is needed. A pioneering study by S group in K reported the CH amidation using CPW valid and the territory cut to derivatives.