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Tools for efficient asymmetric synthesis: design, synthesis and application of fluorous oxazolidinone chiral auxiliaries

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dc.contributor.supervisor Dr. Hultin, Philip G. (Chemistry) en
dc.contributor.author Hein, Jason Ellis
dc.date.accessioned 2006-01-06T20:02:43Z
dc.date.available 2006-01-06T20:02:43Z
dc.date.issued 2006-01-06T20:02:43Z
dc.identifier.citation Hein, J. E.; Geary, L. M.; Jaworski, A. A.; Hultin, P. G.; J. Org. Chem., 2005, 70, 9940-9946. en
dc.identifier.citation Hein, J. E.; Hultin, P. G.; Tetrahedron Asymm., 2005, 13, 2341-2347. en
dc.identifier.citation Hein, J. E.; Zimmerman, J.; Sibi, M. P.; Hultin, P. G.; Org. Lett., 2005, 7, 2755 – 2758. en
dc.identifier.citation Hein, J. E.; Hultin, P. G.; Synlett, 2003, 5, 635-638. en
dc.identifier.uri http://hdl.handle.net/1993/187
dc.description.abstract A new class of oxazolidinone chiral auxiliary has been synthesized from various α-amino acids, incorporating a perfluoroalkyl functional chain as a soluble support. This feature allows the chiral auxiliaries to be employed under standard solution-phase reaction conditions, and rapidly purified from crude mixtures using fluorous solid phase extraction (FSPE). Our investigation of these new materials has been divided into two main sections. To obtain the chiral auxiliaries in multi-gram quantities a synthetic protocol was designed, where efficiency and reproducibility were the primary objectives. Meeting these goals required an extensive study of the reactivity of perfluoroalkyl nucleophiles. This study identified a versatile and scalable protocol for the perfluoroalkylation of the required amino acid starting materials. These results have allowed us to design a general, five-step synthetic pathway to create the fluorous chiral auxiliaries quickly and effectively. The new auxiliaries were then applied in several model reactions, specifically chosen to examine the reactivity and behavior of these compounds. In particular, the auxiliaries were tested for their stereoselectivity, recyclability, and ease of purification, in a series of Aldol reactions, 1,3 dipolar cycloadditions, and radical conjugate additions. This set of model reactions, combined with the facile and efficient synthesis clearly demonstrates that these new chiral auxiliaries are useful alternatives to the non-fluorous oxazolidinone chiral auxiliaries currently employed in stoichiometric asymmetric syntheses. en
dc.format.extent 7405667 bytes
dc.format.mimetype application/pdf
dc.language.iso en_US
dc.subject Fluorous chiral auxiliary en
dc.subject asymmetric synthesis en
dc.subject organic chemistry en
dc.subject oxazolidinones en
dc.subject aldol reactions en
dc.title Tools for efficient asymmetric synthesis: design, synthesis and application of fluorous oxazolidinone chiral auxiliaries en
dc.type Electronic Thesis or Dissertation en
dc.degree.discipline Chemistry en
dc.contributor.examiningcommittee Dr. Hunter, Norm (Chemistry) Dr. Schweizer, Frank (Chemistry) Dr. McIntosh, Alan (Pharmacy) Dr. Curran, Dennis P. (University of Pittsburgh, Chemistry) en
dc.degree.level Doctor of Philosophy (Ph.D.) en
dc.description.note February 2006 en


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