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Stereoselective Olefin Metathesis Processes Using Cyclometalated Ruthenium Alkylidene Complexes

Citation

Rosebrugh, Lauren Estelle (2017) Stereoselective Olefin Metathesis Processes Using Cyclometalated Ruthenium Alkylidene Complexes. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9C53HVW. http://resolver.caltech.edu/CaltechTHESIS:01062017-172749049

Abstract

The recent development of a class of Z-selective ruthenium metathesis catalysts containing a crucial cyclometalated N-heterocyclic carbene (NHC) ligand has extended the applicability of ruthenium-mediated olefin metathesis to the production of a variety of useful Z-olefin-containing small molecules, polymers, and natural products. This thesis explores the synthesis and application of a number of novel Z-selective cyclometalated ruthenium alkylidene complexes displaying enhanced activity and selectivity across a range of metathesis transformations. Mechanistic investigations aimed at understanding and controlling stereoselectivity specifically in ring-opening metathesis polymerization (ROMP) are also detailed.

Chapter 2 describes the preparation of new Z-selective cyclometalated ruthenium metathesis catalysts via an improved method employing sodium carboxylates. Effects of the cyclometalated NHC ligand on catalyst activity and selectivity in several cross metathesis assays, as well as macrocyclic ring-closing metathesis and other industrially relevant transformations, are investigated.

Chapter 3 relates a story in two parts: the first details the synthesis and activity of a series of novel cyclometalated ruthenium alkylidenes displaying unprecedented cis,syndio-selectivity in the ROMP of norbornene- and norbornadiene-derived monomers. The second comprises an extensive study into the origins of stereoselectivity in ROMP in these and related cyclometalated ruthenium initiators. Experimental results are used in conjunction with a computational analysis of propagation transition states to develop a complete stereochemical model for cis,syndio-selctivity in these systems.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Olefin Metathesis, Ruthenium, Stereoselectivity, Z-Selectivity, Catalyst Development, Mechanistic Studies, Ring-Opening Metathesis Polymerization, ROMP
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Grubbs, Robert H.
Thesis Committee:
  • Tirrell, David A. (chair)
  • Grubbs, Robert H.
  • Gray, Harry B.
  • Rees, Douglas C.
Defense Date:7 December 2016
Non-Caltech Author Email:lrosebrugh (AT) gmail.com
Funders:
Funding AgencyGrant Number
National Science Foundation (NSF)CHE-1212767
National Institutes of Health (NIH)R01-GM031332
Office of Naval Research (ONR)N000141310895
National Defense Science and Engineering Graduate FellowshipUNSPECIFIED
Record Number:CaltechTHESIS:01062017-172749049
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:01062017-172749049
DOI:10.7907/Z9C53HVW
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1007/3418_2014_76DOIBook chapter adapted for Chapter 1
http://dx.doi.org/10.1021/ja311916mDOIArticle adapted for Chapter 2
http://dx.doi.org/10.1021/ja405559yDOIArticle adapted for Chapter 3
http://dx.doi.org/10.1021/jacs.5b12277DOIArticle adapted for Chapter 3
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10005
Collection:CaltechTHESIS
Deposited By: Lauren Rosebrugh
Deposited On:20 Jan 2017 17:59
Last Modified:26 Jan 2017 18:23

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