From reactants to products via simple hydrogen-bonding networks: Information transmission in chemical reactions.
The transmission of information is ubiquitous in nature and often occurs through supramolecular hydrogen bonding processes. Here we report that there is a remarkable correlation during synthesis between the efficiency of the hydrogen-bond-directed assembly of peptide-based [2]rotaxanes and the symmetry distortion of the macrocycle in the structure of the final product. It transpires that the ability of the flexible macrocycle-precursor to wrap around an unsymmetrical hydrogen bonding template affects both the reaction yield and a quantifiable measure of the symmetry distortion of the macrocycle in the product. When the yields of peptide rotaxane-forming reactions are high, so is the symmetry distortion in the macrocycle; when the yields are low, indicating a poor fit between the components, the macrocycle symmetry is relatively unaffected by the thread. Thus during a synthetic sequence, as in complex biological assembly processes, hydrogen bonding can code and transmit "information"--in this case a distortion from symmetry--between chemical entities by means of a supramolecularly driven multicomponent assembly process. If this phenomenon is general, it could have far reaching consequences for the use of supramolecular-directed reactions in organic chemistry.
Brancato
Giuseppe
G
Dipartimento di Chimica G. Ciamician, Università degli Studi di Bologna, via F. Selmi n.2, 40126, Bologna, Italy.
Coutrot
Frédéric
F
Leigh
David A
DA
Murphy
Aden
A
Wong
Jenny K Y
JK
Zerbetto
Francesco
F
D002621:Chemistry / Q000379:methods; D005998:Glycine / Q000737:chemistry; D006860:Hydrogen Bonding; D046911:Macromolecular Substances; D008956:Models, Chemical; D008958:Models, Molecular; D008962:Models, Theoretical; D043862:Rotaxanes
D046911:Macromolecular Substances; D043862:Rotaxanes; D005998:Glycine