Executive Summary : | Organic synthesis aims to achieve maximum relevant complexity increase while minimizing step count. Two ways to achieve this are strategy-level reactions, such as pericyclic reactions, which allow for a great increase in target-relevant complexity in one step, and multistep processes, such as tandem/cascade and domino processes, which produce similar or greater complexity changes in one-pot operation. To minimize environmental risk and waste generation, a'reagentless approach' is proposed for a one-pot conversion of quinol to p-benzoquinone using electrochemistry followed by a Diels-Alder reaction using heat. The proposal explores an in-situ generation of p-benzoquinone using electrochemistry, which can attain an exact oxidation potential by changing electricity. The biological profiles of naturally occurring architecturally intriguing taiwaniadducts (tetraterpenoids) have led to the development of'reagentless chemical processes' as a key strategy for the total syntheses of these complex targets from easily available starting materials. The proposed approach includes developing a'reagentless strategy' based on an oxidative Diels-Alder reaction for the total syntheses of taiwaniadducts B, C, H, and I, a reagentless biomimetic for the total synthesis of taiwaniadducts E, F, and G, and a'reagentless cascade' based on an oxidative Diels-Alder reaction followed by a [2+2]-cycloaddition for the biomimetic total synthesis of taiwaniadduct J. This proposal is not only interesting for sustainable development but also in the context of drug discovery programs. |