Expanding cavitand chemistry: the preparation and characterization of [n]cavitands with n>=4.
The preparation of cavitands composed of 4, 5, 6, and 7 aromatic subunits ([n]cavitands, n=4-7) is described. The simple, two-step synthetic procedure utilized readily available starting materials (2-methylresorcinol and diethoxymethane). The two cavitand products having 4 and 5 aromatic subunits exhibited highly symmetric cone conformations, while the larger cavitands (n = 6 and 7) adopt conformations of lower symmetry. 1H NMR spectroscopic studies of [6]cavitand and [7]cavitand revealed that these hosts undergo exchange between equivalent conformations at room temperature. The departure of these two cavitands from cone conformations is related to steric crowding on their Ar-O-CH2-OAr bridges and is predicted by simple molecular mechanics calculations (MM2 force field). X-ray diffraction studies on single crystals of the [4]cavitand, [5]cavitand, and [6]cavitand hosts afforded additional experimental support for these conclusions.
Naumann
C
C
Department of Chemistry, University of British Columbia, Vancouver, Canada.
Román
E
E
Peinador
C
C
Ren
T
T
Patrick
B O
BO
Kaifer
A E
AE
Sherman
J C
JC
D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D012118:Resorcinols / Q000138:chemical synthesis* / Q000737:chemistry
D004988:Ethers, Cyclic; D012118:Resorcinols; C426323:cavitand 4; C426324:cavitand 5; C426325:cavitand 6; C426326:cavitand 7; C049083:2-methylresorcinol