Thesis advisor: James P. Morken / This dissertation will discuss the development of three methodologies for the enantioselective synthesis of organoboron compounds. The first chapter will discuss the initial discovery and development of a palladium-catalyzed reaction that enables the combination of an organolithium, an organoboronic ester and C(sp2)-OTf electrophiles in an enantioselective fashion. This conjunctive cross-coupling takes place through a 1,2-metallate shift which is induced from an alkenylboron ‘ate’ species through interaction with the palladium catalyst. The second chapter of this manuscript will discuss the development of the first nickel-catalyzed version of the conjunctive cross- coupling reaction, which operates enantioselectively with in situ generated 9-BBN boranes. The third and last chapter will discuss the development of complementary method to the conjunctive cross-coupling which enables the enantioselective addition of organozinc reagents and alkyl halides across alkenylboronic esters. This system departs from the metal-induced 1,2-metallate shift mode of reactivity in favor of a Ni- catalyzed radical/addition cross-coupling cascade reaction. This process can be operated in both an inter- and intra-molecular fashion to afford enantiomerically-enriched alkylboronic ester compounds. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
| Identifer | oai:union.ndltd.org:BOSTON/oai:dlib.bc.edu:bc-ir_108653 |
| Date | January 2019 |
| Creators | Chierchia, Matteo Paolo |
| Publisher | Boston College |
| Source Sets | Boston College |
| Language | English |
| Detected Language | English |
| Type | Text, thesis |
| Format | electronic, application/pdf |
| Rights | Copyright is held by the author, with all rights reserved, unless otherwise noted. |
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