2026-09-20T21:18:00Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/113121 2023-07-11 col_2142_5131 col_2142_14789 com_2142_5130 com_2142_14788 com_2142_8903

Sarlah, David Sarlah, David Denmark, Scott E. White, M. Christina Silverman, Scott K. Dennis, David Gerald 2022-01-12T22:34:44Z 2022-01-12T22:34:44Z 2024-01-12T22:35:30Z 2021-06-21 2021-08 Anthracyclines are archetypal representatives of tetracyclic type II polyketide natural products that are widely used in cancer chemotherapy. Although syntheses of this class of compounds have been extensively explored, all known approaches are based on annulations, relying on the union of properly pre-functionalized building blocks. To complement these studies, here we showcase an alternative, non-annulative entry to anthracyclines, starting from a polynuclear arene. Specifically, tetracene was converted to idarubicinone, an aglycone of the FDA approved anthracycline idarubicin, by a judicious orchestration of Co- and Ru-catalyzed arene oxidation and a novel dearomative hydroboration. This global functionalization strategy, a combination of site-selective arene- and dearomative-functionalizations, provided the key anthracycline framework in five operations and enabled rapid and controlled access to idarubicinone. Another class of compound deriving from polyketide synthases are the cannabinoids. Having a long history of use, yet controversial nature Cannabis offers the possibility for the treatment of many diseases. Reports are varied, however, possibly due to the affect of numerous and under-studied minor cannabinoids. A small library of minor cannabinoids were prepared and tested for their anti-inflammatory pain with the goal of discovering a novel lead compound. Specifically, cannabimovone was prepared in biomimetic fashion and displayed a remarkable ability to stimulate the production of cytokines in a BV-2 mouse microglial cell line under inflammatory response. Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-08-01 The student, David Dennis, accepted the attached license on 2021-06-11 at 09:03. The student, David Dennis, submitted this Dissertation for approval on 2021-06-11 at 09:10. This Dissertation was approved for publication on 2021-06-21 at 09:46. DSpace SAF Submission Ingestion Package generated from Vireo submission #16682 on 2022-01-12 at 12:52:13 Made available in DSpace on 2022-01-12T22:34:44Z (GMT). No. of bitstreams: 2 DENNIS-DISSERTATION-2021.pdf: 16329962 bytes, checksum: 1804455104bcd21de2ab9a216d8b63e8 (MD5) LICENSE.txt: 4209 bytes, checksum: 4194646e711564bbb5e24d8c181a21a3 (MD5) Previous issue date: 2021-06-21 Embargo set by: Seth Robbins for item 121047 Lift date: 2024-01-12T22:35:30Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system U of I Only application/pdf http://hdl.handle.net/2142/113121 en Copyright 2021 David Dennis Dearomatization Arenophile Total Synthesis Cannabinoids Cannabis Hydroboration CBD Dearomative hydroboration-enabled synthesis of idarubicinone and synthesis of minor cannabinoids and their metabolites text Thesis Chemistry Chemistry University of Illinois at Urbana-Champaign Dissertation Ph.D.