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Multicomponent Radical Reactions Incorporating Heteroatom-Carbon Bonds Via Polarity-Reversal Cascades

Buquoi, John Q, III

Abstract Details

2019, Doctor of Philosophy, Ohio State University, Chemistry.
Multicomponent reactions (MCRs) have a long, distinguished history beginning in the early 1900’s. While a vast majority of these reactions have followed traditional two-electron pathways, a smaller percentage have proceeded through one-electron mechanisms. Concerning radical MCRs, one finds that the formation of sequential carbon-carbon bonds is the prevalent transformation achieved. Recently, synthetic chemists have begun to incorporate heteroatom-carbon bonds – either through the initiating or terminating partners – into their MCRs. The main focus of this dissertation is the discovery and exploration of new initiating nitrogen and phosphinyl radicals which can be incorporated into MCRs via addition across alkenes and terminating with medicinally relevant heteroarene traps. Chapter 1 details a brief history of MCRs, followed by a summary of the Minisci-2-component reaction and an overview on current trends in Minisci MCRs. Additionally, the electrophilicity of radicals and the important roles that they play is covered, and an overview of the radical classes explored in this thesis is discussed. Chapter 2 describes an investigation of three-component Minisci reactions generated by a unified iodane strategy. Three different initiating radicals are highlighted and shown to be efficient coupling partners in the reactions explored and over 27 new quinolines and isoquinolines were synthesized – emphasizing the broad and general scope of the methodology discovered. Finally, Chapter 3 describes the design and discovery of a photocatalytic system exclusively focused on phosphine oxides and phosphine sulfides. The scope of the phosphinyl radicals, alkenes, and heteroarene traps is more fully explored, ultimately allowing coupling to >30 quinolines and isoquinolines, as well as pyridines – a valuable, but difficult class of compounds to functionalize.
David Nagib (Advisor)
Jovica Badjic (Committee Member)
Craig Forsyth (Committee Member)
Casey Wade (Committee Member)
152 p.

Recommended Citations

Citations

  • Buquoi, III, J. Q. (2019). Multicomponent Radical Reactions Incorporating Heteroatom-Carbon Bonds Via Polarity-Reversal Cascades [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1574348050305556

    APA Style (7th edition)

  • Buquoi, III, John. Multicomponent Radical Reactions Incorporating Heteroatom-Carbon Bonds Via Polarity-Reversal Cascades. 2019. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1574348050305556.

    MLA Style (8th edition)

  • Buquoi, III, John. "Multicomponent Radical Reactions Incorporating Heteroatom-Carbon Bonds Via Polarity-Reversal Cascades." Doctoral dissertation, Ohio State University, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=osu1574348050305556

    Chicago Manual of Style (17th edition)