title: Modulation of an n→π* interaction with α-fluoro groups.
abstract: Noncovalent interactions play an essential role in biological and chemical processes. In the main chain of common protein secondary structures, the lone pair (n) of a carbonyl oxygen is delocalized into the antibonding orbital (π*) of the subsequent carbonyl group. Herein, experimental and computational data reveal that this n→π* interaction can be attenuated by the inductive electron withdrawal of one or two α-fluoro groups in the donor. The steric effect of three α-fluoro groups, however, overcomes the inductive withdrawal. These data evoke a means to modulate the n→π* interaction in peptides, proteins, and other systems.
authors.forename: Amit
authors.initials: A
authors.lastname: Choudhary
authors.forename: Charles G
authors.initials: CG
authors.lastname: Fry
authors.forename: Ronald T
authors.initials: RT
authors.lastname: Raines