Special Seminar

Robert Martin, Princeton University presents "Synthesizing Computations and Experiments for
Functionalizations and Cross-Couplings"

Abstract: The development of novel organic synthetic methodologies en route to complex small
molecules is vital to driving discovery of new materials, dyes, fragrances, and pharmaceuticals.
Transition-metal catalysis and metallaphotoredox catalysis have given rise to novel strategies for cross-
coupling and functionalization of naturally abundant and synthetically practical functional groups,
including alcohols, alkenes, alkanes, and arenes, among others. Computational modeling of organic
reactions, when used in tandem with experiments, provides useful insights into reaction mechanisms
and allows for cheaper and faster predictions of reactivity trends. Recently, we have reported an arene
C—H alkylation by radical-radical cross-coupling, enabling rapid C(sp3)—C(sp2) bond formation
from common alcohol and arene precursors. We have performed Density Functional Theory (DFT)
calculations to determine the branching mechanistic pathways for this transformation and the origins
of heteroselectivity of the cross-coupling. We have further developed a novel piecewise synthesis of
vinyl bromides and alkenes from common ketone and alcohol starting materials. I will discuss these
projects and some future proposals for synergistic experimental and computational approaches to
various problems in organic synthesis.

Biography: Robert was born and raised in Silver Spring, Maryland. He earned his Ph.D. in Chemistry from the
University of Maryland, College Park for his computational studies of transition metal-catalyzed and photocatalyzed
organic transformations. He joined the MacMillan lab in August 2023 as an NSF MPS-Ascend Fellow to gain hands-
on experience and perspective in the field of organic synthesis.