Earl L. Muetterties Lecture: Homogeneous Catalysis for Organic Synthesis and Polymer Synthesis

Seminar | September 20 | 4-5 p.m. | 120 Latimer Hall

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

 College of Chemistry

In order to avoid the formation of undesired by-products, development of catalytic reactions affording the desired compound as a sole product is highly desired. We have developed catalysts applicable for small molecules and macromolecules. The former is recognized as organic synthesis which finds its applications as intermediates for fine chemicals while the latter are widely used in bulk material synthesis. The catalysts we studied are organometallic complexes consist of metals with catalytic activities and ligands with ability to control the reactions. Three examples are shown as below.

(1) Asymmetric synthesis of chiral polymers1,2
Two examples are presented for the synthesis of optically active polymers with main-chain chirality from achiral monomers using chiral metal-complexes as catalysts. Asymmetric alternating copolymerization of α-olefins with carbon monoxide provided optically active polyketones with high enantioselectivity.

(2) Copolymerization of ethylene or propylene with polar vinyl monomers3,4,5
Aiming to expand the application range of polyolefins, metal-catalyzed copolymerization of olefins with easily available polar vinyl monomers has been intensively studied in the last decades. Here in this presentation, our contribution to the development of coordination–insertion copolymerization of ethylene or propylene with polar vinyl monomers by palladium catalysts will be presented.

(3) Organic synthesis with polymerization catalyst6
Propylene polymerization catalyst was successfully used for the total synthesis of a natural product endowed with deoxypropionate unit.

References
[1] Review and accounts articles: (a) Nozaki,K. J. Polym. Sci., Part A: Polym. Chem., 2004, 42, 215-221. (b) Nozaki, K. Pure Appl. Chem., 2004, 76, 541-546.
[2] Recent publications: Nakamura, A.; Kageyama, T.; Goto, H.; Carrow, B. P.; Ito, S.; Nozaki, K. J. Am. Chem. Soc., 2012, 134, 12366-12369.
[3] Review and accounts articles: (a) Nakamura, A.; Anselment, T. M. J.; Claverie, J.; Goodall, B.; Jordan, R. F.; Mecking, S.: Rieger, B.; Sen, A.; van Leeuwen, P. W. N. M.; Nozaki, K. Acc. Che. Res. 2013, 46, 1438-1449. (b) Nakamura, A.; Ito, S.; Nozaki, K. Chem. Rev., 2009, 109, 5215-5244. (c) Carrow, B. P.; Nozaki, K. Macromolecules, 2014, 47, 2541-2555
[4] Recent publications: (a) Carrow, B. P.; Nozaki, K. J. Am. Chem. Soc. 2012, 134, 8802–8805. (b) Nakano, R.; Nozaki, K. J. Am. Chem. Soc., 2015, 137, 10934-10937. (c) Ota, Y.; Ito, S.; Kobayashi, M.; Kitade, S.; Sakata, K.; Tayano, T.; Nozaki, K. Angew. Chem. Int. Ed., 2016, 55, 7505-7509. (d) H. Yasuda, R. Nakano, S. Ito, K. Nozaki, J. Am. Chem. Soc. 2018, 140, 1876–1883.
[5] X. Wang, K. Nozaki, J. Am. Chem. Soc., 2018, 140, 15635–15640.
[6] (a) Ota, Y.; Murayama, T.; Nozaki, K. Proc. Natl. Acad. Sci. USA, 2016, 113, 2857-2861. (b) T. Murayama, K. Nozaki, Angew. Chem. Int. Ed., 2018, 57, 11394–11398.

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