Strained bonds1 provide unique opportunities for the construction of complex molecules, the design of new therapies and the preparation of high-value materials. Targeted release of the potential energy locked in high energy molecular constructs provides a particularly appealing approach to the chemoselective modification of complex biomolecules. Indeed, concepts such as ring strain have become hallmarks of modern bioorthogonal chemistry—perhaps best exemplified in the application of cyclooctynes in strain-promoted cycloadditions.2
This presentation will focus on harnessing ring strain for the development of new synthetic methods aimed at the targeted modification of amino acids and peptides.3-5 The rapid synthesis of a valuable toolbox of highly-strained electrophiles featuring the bicyclobutane motif will be detailed,3 and the utility of these compounds for the strain-release functionalization of both proteinogenic4 and non-proteinogenic5 modalities through alkylation and cycloaddition strategies will be examined.