Synthesis and chiroptical properties of cryptophanes having C1-symmetry.
New enantiopure cryptophanes 3-7 having C(1)-symmetry have been synthesized. Electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) have been used to investigate their chiroptical properties, and the results are compared to those obtained for cryptophane-A (1) having D(3)-symmetry. The ECD spectra of compounds 3-7 show Cotton effects that differ from those of cryptophane-A. However, our results suggest that a confident determination of the absolute configuration of the monofunctionalized cryptophanes can be made using ECD spectroscopy. Interestingly, we have found that the ECD spectra of cryptophanes, especially the (1)L(b) transition, are very sensitive to the nature of the solvent. These spectral modifications are essentially due to bulk solvent properties rather than the ability of a particular solvent to insert into the cavity of cryptophanes. On the other hand, VCD spectra of the monofunctionalized cryptophanes have not revealed significant spectral modifications with respect to the VCD spectrum of the CHCl(3) at cryptophane-A complex, except for CHCl(3) at 7 and to a smaller extent for CHCl(3) at 6. These spectral modifications, which essentially consist in lower intensities of VCD bands associated with the cryptophane backbone, were perfectly reproduced by ab initio calculations performed at DFT (B3PW91/6-31G*) level. These results clearly demonstrate that VCD measurements associated with DFT calculations allow an easy determination of the absolute configuration of cryptophane-A derivatives.
Institut des Sciences Moléculaires, UMR 5255 du CNRS, Université Bordeaux I, 351 Cours de la Libération, 33405 Talence, France.
Dominique
D
Cavagnat
Thierry
T
Buffeteau
Thierry
T
Brotin
D002942:Circular Dichroism; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D046911:Macromolecular Substances / Q000138:chemical synthesis* / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D011083:Polycyclic Compounds; D013237:Stereoisomerism; D014230:Triazoles / Q000138:chemical synthesis* / Q000737:chemistry*; D014732:Vibration
D047028:Macrocyclic Compounds; D046911:Macromolecular Substances; D011083:Polycyclic Compounds; D014230:Triazoles; C523242:cryptophane