HOST GUEST COMPLEXATION .60. RIGIDLY HOLLOW HOSTS THAT ENCAPSULATE SMALL MOLECULES

被引:24
作者
TANNER, ME [1 ]
KNOBLER, CB [1 ]
CRAM, DJ [1 ]
机构
[1] UNIV CALIF LOS ANGELES,DEPT CHEM & BIOCHEM,LOS ANGELES,CA 90024
关键词
D O I
10.1021/jo00027a011
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
New chiral host systems 1 and 2 possessing C3 symmetry have been designed and synthesized. Molecular models of 1 and 2 indicate they contain small enforced cavities and three portals complementary to small molecules. The crystal structure of 1.2CH3CN shows one molecule of CH3CN is encapsulated and the second exists as a solvate. A crystal structure of 2.2CH3OH shows one CH3OH molecule is encapsulated and a second serves as a solvate. A crystal structure of 2.CH2Cl2 shows the host to be empty and that the CH2Cl2 acts as a solvate to provide (by disorder) a C3 pattern about the C3 axis of the host. In CDCl3 solutions (CDCl3 is too large to occupy its cavity), 1 complexed O2, N2, H2O, and CO2 readily and reversibly (H-1 NMR spectra), particularly at low temperatures. In CDCl3 solution, 1 binds CH3OH with K(a) = 10 M-1, DELTA-G-degrees 295 = -1.4 kcal mol-1, DELTA-H congruent-to -6.6 kcal mol-1, and DELTA-S congruent-to -18 cal mol-1 K-1. It also binds CH3CN, but much more weakly. Triamine 2 in CDCl3 binds O2, N2, and H2O weakly and CH3OH with a K(a) = 47 M-1, DELTA-G-degrees 295 = -2.3 kcal mol-1, DELTA-H congruent-to -8.5 kcal mol-1, and DELTA-S congruent-to -21 cal mol-1 K-1. This host binds CH3CN at 295 K with a K(a) in the range of 1-10 M-1, and CH3CH2OH with a K(a) < 5 M-1. The H-1 NMR signals of the guest's CH2 group of 2.CH3CH2OH indicate the protons to be diastereotopic. The half-life for decomplexation of 2.CH3CH2OH was about 40 min at 25-degrees-C.
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页码:40 / 46
页数:7
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