Thesis advisor: James P. Morken / Detailed within this dissertation are three new reactions involving allylboron reagents. Chapter 1 describes the development of Pd-catalyzed allyl-allyl cross-coupling for the preparation of enantioenriched all-carbon quaternary stereogenic centers. This methodology represents a novel approach to a significant challenge for synthetic chemists. Subsequently, an allyl-allyl cross-coupling is described which generates functionally differentiated 1,5-dienes. Such structures allow for several chemoselective manipulations, which add a significant practical note to this cross-coupling methodology. Chapter 2 details the development of the allylboration of nitrosobenzene with (Z)-crotylboronate derivatives, which results in the formation of branched allylic alcohols. This methodology provides a regioselective complement to standard boron oxidation conditions. / Thesis (PhD) — Boston College, 2012. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James P. Morken / The Suzuki-Miyaura cross-coupling reaction is a common strategy for the formation of a new carbon-carbon bond in organic synthesis. However, intramolecular coupling of allylboron ester and aryl electrophiles has never been reported. Herein, Pd-catalyzed intramolecular cross-coupling of allylboronic pinacol ester and vinyl or aryl bromides is presented. Pt-catalyzed 1,2-diboration of 1,3-dienes give α-chiral bis-allylboronic esters, which can undergo diastereoselective additions to carbonyl electrophiles tethered to vinyl or aryl halides to generate a new allylboronic ester moiety. Under Suzuki coupling conditions, the allylboronic esters moiety and the vinyl bromides in the allylation products can cross-couple in an intramolecular fashion to afford highly substituted four-, five-, and six-membered rings with excellent yields and moderate diastereoselectivity. / Thesis (MS) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.