Selective synthesis using oxygen in the air

June 26, 2024

Synthesis of γ-lactones comprising vicinal tetrasubstituted carbon centers

A joint research group of researchers from the RIKEN CSRS and Ritsumeikan University successfully synthesized γ-lactones containing two vicinal tetrasubstituted carbons at the C3 and C4 positions using atmospheric oxygen as an oxidant.

Oxidation is an essential reaction responsible for more than 30% of chemical industrial processes. Oxygen, abundant in the air, has been attracting attention as a clean oxidant. However, because oxygen is stable, using it as an oxidant under mild acid-base conditions is challenging. Additionally, under radical reaction conditions, oxygen converts into reactive oxygen species, making it difficult to control the reactivity. Furthermore, to avoid the risk of explosions, it is desirable to utilize atmospheric oxygen rather than concentrated oxygen.

In this study, the research group achieved the synthesis of γ-lactone with two contiguous tetrasubstituted carbons using radical cyclization/oxygen addition as a key step. They also demonstrated that the newly synthesized γ-lactones can be converted into various derivatives. Furthermore, they computationally revealed the mechanism of how the contiguous tetrasubstituted carbons in the γ-lactone is selectively constructed.

The results of this study are expected to contribute to the selective synthesis of complicated molecules through aerobic oxygenation.

Original article

Angewandte Chemie International Edition doi: 10.1002/anie.202405876

F. Pünner, Y. Sohtome, Y. Lyu, D. Hashizume, M. Akakabe, M. Yoshimura, Y. Yashiroda, M. Yoshida, M. Sodeoka,

"Catalytic Aerobic Carbooxygenation for Construction of Vicinal Tetrasubstituted Centers: Application to the Synthesis of Hexa-substituted γ-Lactones".

Contact

Yoshihiro Sohtome; Visiting Scientist
Mikiko Sodeoka; Group Director
Catalysis and Integrated Research Group