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Dissertation Mike Holmes.pdf (16.33 MB)

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The Synthesis And Characterization Of Novel Chiral Gold(I) N-Heterocyclic Carbene Complexes

Holmes, Michael R, II
http://rave.ohiolink.edu/etdc/view?acc_num=miami1437737871

Abstract Details

2015, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Gold(I) catalysis is a rapidly growing field, showing promise for application to any number of synthetic strategies. Currently, gold(I) catalysts are primarily found in two flavors, phosphine-based ligands, or ligands made from N-Heterocyclic carbenes. While NHC-ligands have distinct advantages, phosphine ligands are more ubiquitous in chiral synthesis and catalysis. This is owing to the linear coordination chemistry of gold(I) and the distance of potential stereocenters from the active site in NHC ligands. Using a novel framework, we have designed a series of chiral gold(I) catalysts featuring sterically tunable ligands. These ligands possess exquisite steric bulk and tunable reactivity. In addition to being a novel design we identified a `through space’ hindrance to biaryl rotation previously unobserved in NHC-metal complexes. Our catalysts also exhibit promising enantioselectivities, competitive with those in the literature. Finally, we have observed and discussed an unprecedented stereoinversion of our chiral products, obtaining an excess of the (S)-enantiomer from an optically pure (R,R)-catalyst that typically gives an (R)-isomer in methoxycyclization reactions.
Benjamin Gung, PhD (Advisor)
Richard Taylor, PhD (Committee Chair)
David Tierney, PhD (Committee Member)
Hong Wang, PhD (Committee Member)
Steven Keller, PhD (Committee Member)
217 p.
Organic Chemistry
Gold Catalysis N-heterocyclic carbenes enantioselective chiral methoxycyclization

Recommended Citations

Citations

  • Holmes, II, M. R. (2015). The Synthesis And Characterization Of Novel Chiral Gold(I) N-Heterocyclic Carbene Complexes [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1437737871

    APA Style (7th edition)

  • Holmes, II, Michael. The Synthesis And Characterization Of Novel Chiral Gold(I) N-Heterocyclic Carbene Complexes. 2015. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1437737871.

    MLA Style (8th edition)

  • Holmes, II, Michael. "The Synthesis And Characterization Of Novel Chiral Gold(I) N-Heterocyclic Carbene Complexes." Doctoral dissertation, Miami University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=miami1437737871

    Chicago Manual of Style (17th edition)

miami1437737871
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© 2015, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.