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51.
52.
The first member of a new class of ditopic calix[6]arene has been synthesized, which is decorated with three N-methylimidazoles at the small rim and three 1,4-disubstituted-1,2,3-triazoles at the large rim. The coordination of a first Zn(II) cation selectively takes place at the small rim. Addition of a second equivalent results in the complexation of the three triazoles, providing a rare example of 1,2,3-triazole ligands embedded within a supramolecular system. 相似文献
53.
Bertram A Maulucci N New OM Mohd Nor SM Pattenden G 《Organic & biomolecular chemistry》2007,5(10):1541-1553
Treatment of a 1 : 1 mixture of the thiazole-based amino acids 8a and 8b with FDPP-i-Pr(2)NEt in CH(3)CN gave a mixture of the cyclic trimers 14, 15, 16 and 17 and the cyclic tetramers 19 and 23 in the ratio 2 : 7 : 5 : 8 : 1 : 1 and in a combined yield of 70%. Separate coupling reactions between the bisimidazole amino acid 45 and the thiazole/oxazole amino acids 43a and 42a in the presence of FDPP-i-Pr(2)NEt led to the bisimidazole based cyclic trimers 55 and 57 respectively (54-57%) and to the cyclic tetramer 56 (8-11%). Similar coupling reactions involving the bisthiazole and bisoxazole amino acids 49 and 47 with the imidazole/oxazole/thiazole amino acids 41a, 42a and 43a gave rise to the library of oxazole, thiazole and imidazole-based cyclic peptides 58, 59, 60, 61, 62, 63, 64 and 65. A coupling reaction between the bisthiazole amino acid 49 and the oxazole amino acid 73 led to an efficient (36% overall) synthesis of bistratamide H (67) found in the ascidian Lissoclinum bistratum. Coupling reactions involving oxazolines with thiazole amino acids were less successful. Thus, a coupling reaction between the phenylalanine-based oxazoline amino acid 71a and either the thiazole amino acid 8a or the bisthiazole amino acid 74 gave only a 2% yield of the cyclic hexapeptide didmolamide A (4) found in the ascidian Didemnum molle. Didmolamide B (68) was obtained in 9% yield from a coupling reaction between 74 and the phenylalanine threonine amino acid 72, using either FDPP or DPPA. 相似文献
54.
Izzet G Zeng X Akdas H Marrot J Reinaud O 《Chemical communications (Cambridge, England)》2007,(8):810-812
A calix[6]arene capped by a tmpa unit provides Cu(ii) funnel complexes that, for the first time, accept not only neutral guest ligands but also anionic ones such as a hydroxide, which is due to a small conformational change in the calixarene cone. 相似文献
55.
Bistri O Mazeau K Auzély-Velty R Sollogoub M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(31):8847-8857
New beta-cyclodextrin (beta-CD) dimeric species have been synthesised in which the two CD moieties are connected by one or two hydrophilic oligo(ethylene oxide) spacers. Their complexation with sodium adamantylacetate (free adamantane) and adamantane-grafted chitosan (AD-chitosan) was then studied by different complementary techniques and compared with their hydrophobic counterparts that contain an octamethylene spacer. Isothermal titration calorimetry experiments have demonstrated that the use of hydrophilic spacers between the two CDs instead of aliphatic chains makes almost all of the CD cavities available for the inclusion of free adamantane. Investigation of the interaction of the CDs with AD-chitosan by viscosity measurements strongly suggests that the molecular conformation of the CD dimeric species plays a crucial role in their cross-linking with the biopolymer. The derivative doubly linked with hydrophilic arms, also called a duplex, has been shown to be a more efficient cross-linking agent than its singly bridged counterpart, referred to as a dimer. Hence, only 0.5 molar equivalents of the hydrophilic duplex with respect to adamantane was required to obtain the maximum viscosity, whereas in the case of the duplex with aliphatic spacers, the maximum viscosity was achieved with a [duplex]/[AD] ratio of about 1.7 (corresponding to a [CD]/[AD] ratio of 2.5), but with a higher value. To clarify the relationships between the molecular architecture and complexation properties, computational studies were also performed that clearly confirmed the importance of double bridging. 相似文献
56.
Eduardo Cortés Erik Peréz Ramírez Olivia García‐Mellado de Cortés 《Journal of heterocyclic chemistry》2007,44(1):189-192
57.
We describe a pair of genetic algorithms for solving two stable matching problems. Both stable matching problems we will consider involve a set of applicants for positions and a set of employers. Each applicant and each employer prepares a rank order list of a subset of the actors in the other set. The goal is to find an assignment of applicants to employers in which if applicant a is not assigned to employer b then either a prefers his assignment to b or b prefers its assignment toa . In other words, no applicant/employer pair can both improve their situations by dropping their current assignments in favor of each other. Our goal will be to enumerate the stable matchings. One of the problems we will consider is the well-known stable marriage problem, in which neither applicant nor employer preference lists are linked. In the other problem, we will allow pairs of applicants who form a couple to submit joint rank order lists of ordered pairs of employers. 相似文献
58.
59.
60.
Zeng X Coquière D Alenda A Garrier E Prangé T Li Y Reinaud O Jabin I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(24):6393-6402
A new C(3v)-symmetrical calix[6]azacryptand, that is, calix[6]tmpa (11), was synthesized by efficient [1+1] macrocyclization reactions. Remarkably, both linear and convergent synthetic strategies that were applied lead to equally good overall yields. Calix[6]tmpa behaves as a single proton sponge and appeared reluctant to undergo polyprotonation, unlike classical tris(2-pyridylmethyl)amine (tmpa) derivatives. It also acts as a good host for ammonium ions. Interestingly, it strongly binds a sodium ion and a neutral guest molecule, such as a urea, an amide, or an alcohol, in a cooperative way. A (1)H NMR study indicated that the ligand, as well as its complexes, adopt a major flattened cone conformation that is the opposite of that observed with the previously reported calix[6]cryptands. Characterization of the monoprotonated derivative 11H(+) by X-ray diffraction also revealed the presence of a 1,3-alternate conformation, which is the first example of its kind in the calix[6]arene family. This conformer is probably also present in solution as a minor species. The important covalent constraint induced by the polyaromatic tmpa cap on the calixarene skeleton, and conversely from the calix core onto the tmpa moiety, is the likely basis for the unique conformational and chemical properties of this host. 相似文献