Expanding the scope of a Diels-Alder approach to biaryl synthesis Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/05741x05r

Descriptions

Attribute NameValues
Creator
Abstract or Summary
  • A Diels-Alder approach to biaryls (DAB) has been applied towards the synthesis of highly substituted, programmable biaryl templates. Tri- and tetra-ortho-substituted biaryls can be produced in just three to four steps from commercially available materials utilizing the Diels-Alder [4+2] cycloaddition. The methods described herein will illustrate the ability of mono and disubstituted aryl acetylenic compounds to perform effectively as dienophiles in the Diels-Alder reaction. Both acyclic and cyclic dienes have been implemented in our DAB process, with the latter requiring milder reaction conditions and exhibiting higher yields. The application of our DAB strategy towards the synthesis of biaryls has provided rapid entry to challenging substitution patterns that are not readily available by traditional coupling methods. Aryl acetylenes that possess aryl / alkyl stannyl substituents undergo the cycloaddition / cycloreversion reaction with bisoxygenated dienes to produce truly programmable biaryl templates that are readily functionalized to give access to compounds that are not readily accessible via traditional methods. Efforts to functionalize these biaryl templates led to the discovery of a novel boroxine-based Suzuki coupling strategy that can efficiently convert the sterically-encumbered chlorine-carbon bond to various aryl and alkyl groups giving rise to functionalized tetra-ortho-substituted biaryls that cannot be produced by traditional metal-mediated aryl-aryl bond formation. The syntheses of three unique tetra-ortho-substituted biaryl compounds were accomplished and these compounds were evaluated as potential ligands in aldol and hetero-Diels-Alder reactions. During the course of this work, a general method for the resolution of the biaryl compounds was illustrated that provided an efficient method for the separation of the atropisomers of our biaryl compounds. In addition, an efficient method for the construction of chiral biaryl amino acids was established. During the course of this work, the ability to construct a biaryl amino acid template was established, and the resolution of this template was accomplished using the chiral amine, brucine. Using this template, we were able to construct a small peptide containing a point-chiral amino acid at the C terminus of the biaryl template.
Resource Type
Date Available
Date Copyright
Date Issued
Degree Level
Degree Name
Degree Field
Degree Grantor
Commencement Year
Advisor
Committee Member
Academic Affiliation
Non-Academic Affiliation
Keyword
Subject
Rights Statement
Language
Replaces
Additional Information
  • description.provenance : Made available in DSpace on 2009-08-18T15:04:09Z (GMT). No. of bitstreams: 1 JPSThesis.pdf: 55333022 bytes, checksum: 8b264585fad24397cbe114a7631afc4e (MD5)
  • description.provenance : Approved for entry into archive by Laura Wilson(laura.wilson@oregonstate.edu) on 2009-08-18T15:04:09Z (GMT) No. of bitstreams: 1 JPSThesis.pdf: 55333022 bytes, checksum: 8b264585fad24397cbe114a7631afc4e (MD5)
  • description.provenance : Submitted by Johanna Schwartz (perkinjo@onid.orst.edu) on 2009-08-13T18:10:45Z No. of bitstreams: 1 JPSThesis.pdf: 55333022 bytes, checksum: 8b264585fad24397cbe114a7631afc4e (MD5)
  • description.provenance : Approved for entry into archive by Julie Kurtz(julie.kurtz@oregonstate.edu) on 2009-08-13T18:31:26Z (GMT) No. of bitstreams: 1 JPSThesis.pdf: 55333022 bytes, checksum: 8b264585fad24397cbe114a7631afc4e (MD5)

Relationships

In Administrative Set:
Last modified: 10/20/2017

Downloadable Content

Download PDF
Citations:

EndNote | Zotero | Mendeley

Items