Inclusion channel

Selenourea [630-10-4] ]5k.e urea and thiomea can form channel inclusion compounds (87) with a variety of hydrocarbons. Though the difference in channel diameter between thiourea and selenourea is small, selenourea seems to be much more selective for the inclusion of certain guest molecules (eg, cis/trans isomers). 

Fig. 3. Channel inclusion compound of deoxycholic acid (6) with acetone. The crystal packing is affected by head-to-tail H-bond-mediated double layers of host molecules (H-bonds as dotted lines, guest molecules shaded) (Adapted from Ref. 13)...

M. D. Hollingsworth, U. Werber-Zwanziger, M. E. Brown, J. D. Chaney, J. C. Huffman, K. D. M. Harris, S. P. Smart, "Spring-loaded at the molecular level relaxation of guest-induced strain in channel inclusion compounds ,/. Am Chem Soc 1999,121, 9732-9733. 

The polymerization of trans-1,3-pentadiene, 149, in a chiral channel inclusion complex with enantiomerically pure perhydrotriphenylene affords an optically active polymer, 150 (236). Asymmetric polymerization of this monomer guest occurs also in deoxycholic acid inclusion complexes (237). 

Cyclotriveratrylene/1180-60-5] (34) is a cyclocondensation product of veratrole with formaldehyde. It possesses a stable trigonal crown conformation and forms crystalline inclusion compounds with benzene, chlorobenzene, toluene, thiophene, decalin, chloroform, acetone, carbon disulfide, acetic acid, and butyric acid (101). Their structures consist of columns of cyclotriveratrylene molecules that are not amenable to close packing and provide channels into which the guests are accommodated. A number of modified host structures, derived from prototype (34) have been prepared. The hexaphenol analogue cyclotricatechylene also yields well-defined channel inclusions (101). They involve mosdy polar guests and the structures are held by hydrogen bonding. 

Figure 7.16 Channel inclusion compounds of di-ol 7.13 with either (a) CC14 or (b) the host molecule itself as guests.

Lahav, Leiserowitz and their coworkers have used inclusion complexes of deoxycholic acid to carry out asymmetric photochemical reactions. The authors reported that acetophenone forms a 2 5 crystalline channel inclusion complex with deoxycholic acid 22 as the host and that irradiation of the complex in th4 solid state leads to abstraction of a hydrogen atom by the acetophenone 23a from C5 of the steroid followed by coupling of the resulting radical pair to produce1 photoproduct 24 (Scheme 9) [216,219]. The authors were able to follow the course of the reaction by x-ray crystallography. Only one diastereomer of the product was obtained in the reaction. Aoyama et al. have studied the reaction of AT,N-dialkylpyruvamides in deoxycholic acid inclusion crystals (Scheme 10) [246], Solid-state irradiation of the inclusion complex of 22 and 25 gave the... 

Since the major driving force of inclusion is hydrophobic interaction, stabilities of ICs depend strongly on the polarity of the polymer. The more hydrophobic the polymer is, the higher is the affinity of CDs towards it. On the other hand, solubility in water decreases with increasing hydrophobicity of the polymer. Since affinity and solubility have to be compromised, an optimum of polarity of the polymer should exist for complexation by CDs. It is difficult to quantify the binding free energies of CD channel inclusion compounds, since they are insoluble in water. Stabilities of these polymeric ICs can be qualitatively compared by competition experiments. For example, PLLA and PCL were competitively included in a-CD. The IC of PCL was... 

II. Classical Channel Inclusion Compounds of Urea, Thiourea, and Selenourea. 155... 

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