We describe the development of the dioxasiline ring as a π-facial directing group for intramolecular Diels−Alder (IMDA) cyclizations. The rigidity of this directing group delivers robust stereocontrol across a number of substrates, affording single diastereomers. While our method readily delivers norbornane ring systems, we will discuss the challenges faced in applying it to the formation of 2,2,2 bicyclic ring systems. Finally, we discuss a deuterium labelling experiment, which reveals that the reactive diene in our IMDA is formed <i>via </i>γ-deprotonation followed by [1,5] hydride shifts.

Silacycle-templated intramolecular Diels–Alder cyclizations for the diastereoselective construction of complex carbon skeletons

ACS Spring 2022

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