UC Irvine

In Chapter One the isolation, biosynthesis, and bioactivity of the anthraquinone–

xanthone heterodimers is discussed. Additionally, a review of previous synthetic efforts

towards this class of natural products is provided, along with reported syntheses of related

anthraquinone- and xanthone-derived natural products.

Chapter Two discusses synthetic efforts towards the anthraquinone–xanthone

heterodimer natural products. This includes model system studies aimed at the construction

of the bicyclo[3.2.2]nonane core, as well as our first generation synthesis of the

benzocycloheptenone precursor. Our optimized route involves the development of an

iodine(III)-mediated arylation enol ethers, which allows for rapid construction of a key

intermediate in the synthesis. A Hauser–Kraus annulation–aldol reaction sequence enables

assembly of the bicyclo[3.2.2]nonane core, which is then carried on to complete the first total

synthesis of acremoxanthone A in 10 steps from commercial material.

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In Chapter Three an overview of previously reported methods for the alkenylation of

ketones is provided, followed by the development of the intermolecular In(III)-catalyzed

alkenylation of silyl enol ethers with alkynes. This reaction is demonstrated on a variety of

cyclic and acyclic substrates to provide the corresponding 2-siloxy-1,4-dienes, via a formal

ene reaction, or β,γ-unsaturated ketones. Additionally, mechanistic investigations are

discussed, including a proposed mechanism for the intermolecular formal ene reaction.