Cavitands with introverted functionality stabilize tetrahedral intermediates.
The synthesis and characterization of two deepened cavitand hosts with introverted functionality--functional groups directed into the cavity--is described. Two functions can be introverted, alcohol and aldehyde, and they show the formation of hemiacetals and hemiketals on binding small guests with complementary functional groups. The structures of the bound hemiacetals are determined by 1D and 2D NMR studies. The arrangements of the guests in the cavitands enhance the equilibrium constants of carbonyl additions, K/K(ctrl), between 13- and 10(5)-fold, compared to their counterparts in solution. The stabilization of the addition products is due to the prior complexation of the guests and the organized solvation provided to the tetrahedral intermediates by a network of secondary amides at the cavitand rim.
Hooley
Richard J
RJ
The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, MB-26, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Restorp
Per
P
Iwasawa
Tetsuo
T
Rebek
Julius
J
D004988:Ethers, Cyclic / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D012118:Resorcinols / Q000737:chemistry*
D004988:Ethers, Cyclic; D012118:Resorcinols; C442939:cavitand