Tug‐of‐War in a Dynamic Helical Peptide: Solvent‐Induced Helix‐Helix Transition of a Lactam‐Bridged Peptide Composed of Point‐ and Axial Chiralities Remote from Each Other

The dynamic axial chirality of oligopeptide‐bound 2,2′‐bipyridine (bpy) residues can be remote‐controlled and diastereoselectively locked. A right‐handed ( P )‐3 10 ‐helix is first induced in the dynamic helical oligopeptide by an l ‐valine ( l ‐Val) far from the bpy moiety and the induced axial bpy chirality is diastereoselectively dioxidized. The resulting l ‐Val‐containing linear oligopeptides at the 3,3′‐positions retain their ( P )‐3 10 ‐helices independent of the axial chirality (a R or a S ) of the N‐terminal N , N′ ‐dioxide‐bpy unit, while a lactam‐bridged dynamic helical oligopeptide exhibits a unique solvent‐induced helix‐helix transition as a result of competitive helix‐inducing biases between the l ‐Val and (a R ) or (a S )‐ N , N′ ‐dioxide‐bpy residues remote from each other along the entire oligopeptide chain in a tug‐of‐war like manner.