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Investigations into the selectivity of olefin cross-metathesis using ruthenium alkylidene catalysts: electronic and steric matching of substrates

Citation

Chatterjee, Arnab Kumar (2003) Investigations into the selectivity of olefin cross-metathesis using ruthenium alkylidene catalysts: electronic and steric matching of substrates. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-09122002-142629

Abstract

Olefin cross-metathesis (CM) is a thermodynamically controlled metathesis reaction that is governed by statistical product distributions and a mixture of olefin stereoisomers. In fact, while the reaction allows for the functionalization of alpha-olefins under mild conditions, it has not been used widely due to a lack of selective processes. The research effort disclosed here has provided some new solutions to the selectivity issues involved with CM. These including the use of olefins with altered steric and electronic properties allowing for selective olefin functionalization by CM. After an introduction to state-of-the-art CM in Chapter 1, the discussion continues with CM work in earlier generation ruthenium catalyst systems (Chapter 2). The next two chapters reveal new substrate scope in CM using more active ruthenium based catalysts developed in this group, including the synthesis of trisubstituted olefins (Chapter 3) and directly functionalized olefins (Chapter 4). Once discoveries in expanding substrate scope were accomplished, the final chapter outlines an empirical model for understanding the electronic and steric factors in CM selectivity across a variety of olefin metathesis catalysts. This model provides a method to determine if selective CM can be performed for target-oriented synthetic efforts. In addition, a better understanding of selectivity issues allows for the discovery of new reaction platforms and expands the synthetic utility of CM. These are discussed in Chapter 5 and describe CM as a method to install structural elements as well as to synthesize reagents for subsequent transformation.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:alkene metathesis; cross-coupling; cross-metathesis; metathesis; ruthenium
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:The Herbert Newby McCoy Award, 2002
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Grubbs, Robert H.
Thesis Committee:
  • Dervan, Peter B. (chair)
  • MacMillan, David W. C.
  • Peters, Jonas C.
  • Grubbs, Robert H.
Defense Date:17 September 2002
Record Number:CaltechETD:etd-09122002-142629
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-09122002-142629
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3492
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:14 Nov 2002
Last Modified:26 Dec 2012 03:00

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