Earl L. Muetterties Lecture: Development of New Catalytic Reactions toward Utilization of Renewable Resources

Seminar | September 27 | 4-5 p.m. | 120 Latimer Hall | Canceled

 Kyoko Nozaki, Department of Chemistry and Biotechnology, The University of Tokyo

 College of Chemistry

Carbon dioxide is one of the most attractive renewable C1 resources, which has many practical advantages such as abundance, economic efficiency, and lack of toxicity. The favorable nature as a carbon source is, however, inextricably linked to its inherent inertness. Here we report a new strategy to circumvent thermodynamic and kinetic barriers for copolymerizations of carbon dioxide and olefins by using a meta-stable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one, which is formed by the palladium-catalyzed condensation of carbon dioxide and 1,3-butadiene. Subsequent free radical polymerization of the lactone intermediate afforded high-molecular-weight polymers with a carbon dioxide content of 33 mol% (29 wt%).1 The obtained polymer consists of a bicyclic repeating unit whose hydrolysis was reversible.2

Unique catalytic behavior of hydroxycyclopentadienyl complexes will be presented. Selective hydrogenolysis of sp2 C–OH bonds in arenols and O–CH3 bonds in aryl methyl ethers by (CpOH)Ir(L)H2 will be presented, implying their potential application for mass production of arenes from lignin or its degraded components.3 Metal-ligand cooperative sp3 C–H bond formation will be also discussed for (CpOH)Pt+(L)Me2.4

1. Nakano, R.; Ito, S.; Nozaki, K. Nature Chem. 2014, 6, 325–331.
2. Moon, S.; Masada, K.; Nozaki, K. J. Am. Chem. Soc. 2019, 141, 10938–10942
3. Kusumoto,S.; Nozaki, K. Nature Commun. 2015, 6, 6296.
4. Higashi, T.; Ando, H.; Kusumoto, S.; Nozaki, K. J. Am. Chem. Soc. 2019, 141, 2247–2250.