Synthesis and host-guest studies of chiral N-linked peptidoresorc[4]arenes.
| Title: | Synthesis and host-guest studies of chiral N-linked peptidoresorc[4]arenes. |
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| Authors: | Botta B; Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Università La Sapienza, P le Aldo Moro 5, 00185, Roma, Italy. bruno.botta@uniroma1.it; D'Acquarica I; Monache GD; Subissati D; Uccello-Barretta G; Mastrini M; Nazzi S; Speranza M |
| Source: | The Journal of organic chemistry [J Org Chem] 2007 Nov 23; Vol. 72 (24), pp. 9283-90. Date of Electronic Publication: 2007 Oct 25. |
| Publication Type: | Journal Article; Research Support, Non-U.S. Gov't |
| Language: | English |
| Journal Info: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 2985193R Publication Model: Print-Electronic Cited Medium: Print ISSN: 0022-3263 (Print) Linking ISSN: 00223263 NLM ISO Abbreviation: J Org Chem Subsets: MEDLINE |
| Imprint Name(s): | Publication: Columbus Oh : American Chemical Society; Original Publication: Easton, Pa. [etc.] |
| MeSH Terms: | Calixarenes/*chemical synthesis ; Peptides/*chemistry ; Resorcinols/*chemistry; Carboxylic Acids/chemistry ; Chlorides/chemistry ; Hydrogen Bonding ; Magnetic Resonance Spectroscopy ; Models, Chemical ; Spectrometry, Mass, Electrospray Ionization |
| Abstract: | Four cone resorc[4]arene octamethyl ethers (10, 11, ent-10, and ent-11) tetrafunctionalized at the feet with valyl-leucine [LL- (6); DD- (ent-6)] and leucyl-valine [LL- (9); DD- (ent-9)] methyl esters have been synthesized. These compounds, obtained by conjugation of macrocycle tetracarboxylic acid chlorides with the appropriate terminal amino groups of the above dipeptides, are N-linked peptidoresorc[4]arenes. We found that these macrocycles (M) are capable of recognizing the homologue dipeptides as guests (G), both in solution and in the gas phase, by forming relatively stable host-guest complexes ([M.G]), resistant to chromatographic purification but not to heating. Complexation phenomena between M and G in solution were investigated by NMR methods, including NMR DOSY experiments, for the detection of translational diffusion. Heteroassociation constants of 2030 and 186 M(-1) were obtained by the Foster-Fyfe method for the complexes [10.6] and [10.ent-6], respectively, the latter being comparable to the self-association constant of dipeptide itself. Conversely, the structural features of the proton-bound complexes [M.H.Gn]+ (n = 1, 2), generated in the gas phase by electrospray ionization mass spectrometry (ESI-MS), were investigated by collision-induced dissociation (CID) experiments. In both cases, the four N-linked peptidoresorc[4]arenes were shown to act as synthetic receptors and to recognize the homologue dipeptide by means of hydrogen bonds. |
| Substance Nomenclature: | 0 (Carboxylic Acids); 0 (Chlorides); 0 (Peptides); 0 (Resorcinols); 130036-26-9 (Calixarenes); YUL4LO94HK (resorcinol) |
| Entry Date(s): | Date Created: 20071026 Date Completed: 20080226 Latest Revision: 20121115 |
| Update Code: | 20260130 |
| DOI: | 10.1021/jo7016636 |
| PMID: | 17958449 |
| Database: | MEDLINE |
Journal Article; Research Support, Non-U.S. Gov't