According to a prevailing theory, (2S,4R)-4-hydroxyproline (Hyp) residues stabilize the collagen triple helix via a stereoelectronic effect that preorganizes appropriate backbone torsion angles for triple-helix formation. This theory is consistent with the marked stability that results from replacing the hydroxyl group with the more electron-withdrawing fluoro group, as in (2S,4R)-4-fluoroproli...

Stereoelectronic effects modulate molecular reactivity and conformation. For example, the nucleophilic attack at a carbonyl carbon is preferred along the B€urgi Dunitz trajectory. This orientational preference stems from a stereoelectronic effect arising from the delocalization of an electron pair (n) of a nucleophile into an antibonding orbital (π*) of the carbonyl group. Our experimental and ...

A new intersection between reaction chemistry and electronic circuitry is emerging from the ultraminiaturization of electronic devices. Over decades chemists have developed a nuanced understanding of stereoelectronics to establish how the electronic properties of molecules relate to their conformation; the recent advent of single-molecule break-junction techniques provides the means to alter th...