Ring-Opening Metathesis of Bulky Norbornene Monomers and the Radical-Mediated Hydrophosphonation of Olefins

Citation

Daeffler, Christopher Scot (2013) Ring-Opening Metathesis of Bulky Norbornene Monomers and the Radical-Mediated Hydrophosphonation of Olefins. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/E7VW-EX09. https://resolver.caltech.edu/CaltechTHESIS:03312013-175520336

Abstract

This thesis discusses two major topics: the ring-opening metathesis polymerization (ROMP) of bulky monomers and the radical-mediated hydrophosphonation of olefins. The research into the ROMP of bulky monomers is further divided into three chapters: wedge-shaped monomers, the alternating copolymerization of 1-methyloxanorbornene derivatives with cyclooctene, and the kinetic resolution polymerization of 1-methyloxanorbornene derivatives. The wedge-shaped monomers can be polymerized into diblock copolymers that possess photonic crystal properties. The alternating copolymerization of 1-methyloxanorbornene derivatives with cyclooctene is performed with > 90% alternation via two different routes: typical alternating copolymerization and a sequence editing approach. The kinetic resolution polymerization of these same 1-methyloxanorbornene monomers achieves only modest selectivity (S=4), but there is evidence that the growing polymer chain forms a helix that influences the selectivity of the resolution. The last topic is the radical-mediated hydrophosphonation of olefins. This synthetic method provides access to Wittig reagents that are capable of highly cis-selective olefinations of aldehydes.

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