Amplification of chirality: the "sergeants and soldiers" principle applied to dynamic hydrogen-bonded assemblies.
The amplification of supramolecular chirality has been studied in dynamic chiral hydrogen-bonded assemblies 1(3).(CA)(6) using "Sergeants and Soldiers" experiments. Previously, we have shown that chiral centers present in either the dimelamine component 1 or the cyanurate component CA quantitatively induce one handedness (M or P) in the assembly. This offers the possibility to study the amplification of chirality under two different kinetic regimes. When chiral dimelamines 1 are used, the exchange of chiral components and (M/P)-interconversion, i.e., interconversion between the (M)- and (P)-isomers of assembly 1(3).(CA)(6), take place via identical pathways (condition A). When chiral cyanurates CA are used, the exchange of chiral components occurs much faster than (M/P)-interconversion (condition B). Experimentally, a much stronger chiral amplification is observed under condition B. For example, the observed chiral amplification for a mixture of chiral and achiral components (40:60) is 46% under condition B and 32% under condition A. Kinetic models were developed to fit the experimental data and to simulate chiral amplification in dynamic systems in general. These simulations show that it is theoretically possible that the diastereomeric excess in a dynamic system is more than 99% with less than 1% chiral component present!
Prins
L J
LJ
Contribution from the Laboratory of Supramolecular Chemistry and Technology, MESA(+) Research Institute, University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands.
Timmerman
P
P
Reinhoudt
D N
DN
D001463:Barbiturates / Q000737:chemistry; D047250:Calixarenes; D006860:Hydrogen Bonding; D007700:Kinetics; D008956:Models, Chemical; D010636:Phenols / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics; D014227:Triazines / Q000737:chemistry
D001463:Barbiturates; D010636:Phenols; D014227:Triazines; C121325:calix(4)arene; D047250:Calixarenes; C004632:cyanuric acid; C011907:melamine; C032232:barbituric acid