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Authors: Chen, Liye
Advisors: Carrow, Brad P
Contributors: Chemistry Department
Keywords: base-free transmetalation
monoligated palladium(0)
Suzuki-Miyaura coupling
Subjects: Organic chemistry
Issue Date: 2018
Publisher: Princeton, NJ : Princeton University
Abstract: Pd-catalyzed cross-coupling, initially developed in the 1970s, has now become an indispensable tool in synthetic chemistry. To extend the current capability of crosscoupling can immensely benefit the practice of organic synthesis. In recent years, ligandaccelerated catalysis has been discovered as an effective strategy to enable challenging cross-coupling reactions. To this end, tri(1-adamantyl)phosphine has been designed and synthesized. The new ligand enabled the development of more sustainable synthetic protocols for industrial chemicals, pharmaceuticals, and materials and the mechanistic investigations of several important catalytic intermediates. Specifically, Chapter 2 describes the synthesis of tri(1-adamantyl)phosphine and detailed characterization of its properties (e.g., stability against cyclometalation, steric, and electronic parameters). Ligand-accelerated Suzuki-Miyaura coupling was demonstrated and found to be generally applicable to many classes of substrates. Results on ligand structure-property relationships inspired the later development of diamondoid phosphines in our laboratory. Chapter 3 details the synthesis of tri(1-adamantyl)phosphine-ligated organopalladium cations, key intermediates in unconventional base-free transmetalation of boronic acids. By decoupling the role of base from transmetalation, we circumvented the protodeboronation of sensitive boron reagents and demonstrated the first general polyfluoroarylation methods of aryl halides and diazonium salts using commercial reagents. These methods enabled rapid access to a wide range of material-like polyfluoroaromatic scaffolds. Finally, in Chapter 4, the first experimental evidence of monoligated palladium(0) complexes in solution is discussed. The generation and structural characterization of such intermediates lend strong credence to previous mechanistic hypothesis and paved the way to more detailed investigations of highly unsaturated “12 e-” palladium(0) species in stoichiometric and catalytic reactions.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog:
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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