Graduate Thesis Or Dissertation

 

Total Synthesis of Tryptamine Alkaloids from the Arundo and Leuconotis Genera Public Deposited

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  • The first part of this manuscript is about the total synthesis of the Arundo donax bis(indole) natural products. The A. donax alkaloids were prepared using the first example of an ynindole Diels–Alder reaction. Each were then separated, isolated, and determined to have stable enantiomeric conformations at room temperature (Chen, J.; Ferreira, A. J.; Beaudry, C. M. Angew. Chem. Int. Ed. 2014, 53, 11931–11934). The Arundo alkaloids bear a hindered C–N biaryl axis which led to a racemization energy barrier sufficiently high that each pair of enantiomers isolated. The rate of racemization (krac), free energy barrier to racemization (DG‡rac), and the corresponding half-lives (t1 2) were experimentally determined for each of the natural products prepared. The DG‡rac values range from 23.3–24.3 kcal mol-1corresponding to t1 2 = 4150–25100 seconds at room temperature. The absolute configuration was determined for each of the alkaloids using circular dichroism (CD) spectroscopy and the exciton chirality method.The second part of this manuscript discloses our findings from a synthetic effort toward the Leuconotis alkaloid leuconoxine. Our strategy made use of a radical translocation-conjugate addition cascade to expediently assemble the tryptamine core of the natural product. Specifically, a vinyl radical was generated from homolysis of a C–Br bond and underwent a 1,5-hydrogen atom abstraction (1,5-HAT) to form an a- amino radical. The free radical intermediate then performed a 5-exo-trig cyclization forming an indoline ring. Preliminary investigations centered around using a 1,6- HAT, which did not result in successful translocation. A 1,4-HAT was also evaluated, but did not lead to the desired bond formation.
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  • description.provenance : Approved for entry into archive by Steven Van Tuyl(steve.vantuyl@oregonstate.edu) on 2017-11-17T00:54:02Z (GMT) No. of bitstreams: 2license_rdf: 1379 bytes, checksum: da3654ba11642cda39be2b66af335aae (MD5)FerreiraAndrewJ2017.pdf: 10533740 bytes, checksum: 48050741d14385180294f21b4689ceae (MD5)
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  • Intellectual Property (patent, etc.)
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  • 2018-01-30 to 2018-11-27

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