Abstract: The first segment of this presentation will detail our development of a methodology to control π-facial selectivity in intramolecular Diels–Alder cyclizations using a silacycle directing group. A panel of substrates is synthesized and tested, providing insight into the capabilities and, more importantly, the limits of the methodology. Deeper mechanistic insight is gained through a deuterium-labelling study, which suggests the role of [1,5] hydride shifts in the formation of the reactive diene. 

Next, our efforts towards the total synthesis of the artemisia sesquiterpenoids artatrovirenols A and B will be discussed. With the goal of investigating the plausibility of a proposed biosynthesis, our synthetic route targets a key intramolecular Diels–Alder cyclization to construct the unprecedented carbon skeleton of these natural products. Beginning from α-santonin, our designed synthetic route is explored, leading to numerous reworkings as a result of roadblocks encountered in the installation of the dienophile moiety. Preliminary experiments towards affecting the key intramolecular Diels–Alder cyclization will be discussed.