Conformations macrocycles

Fu N, Baumes JM, Arunkumar E, Noll BC, Smith BD (2009) Squaraine rotaxanes with boat conformation macrocycles. J Org Chem 74 6462-6468... 

Cyclodextrins are macrocyclic compounds comprised of D-glucose bonded through 1,4-a-linkages and produced enzymatically from starch. The greek letter which proceeds the name indicates the number of glucose units incorporated in the CD (eg, a = 6, /5 = 7, 7 = 8, etc). Cyclodextrins are toroidal shaped molecules with a relatively hydrophobic internal cavity (Fig. 6). The exterior is relatively hydrophilic because of the presence of the primary and secondary hydroxyls. The primary C-6 hydroxyls are free to rotate and can partially block the CD cavity from one end. The mouth of the opposite end of the CD cavity is encircled by the C-2 and C-3 secondary hydroxyls. The restricted conformational freedom and orientation of these secondary hydroxyls is thought to be responsible for the chiral recognition inherent in these molecules (77). 

An interesting use of the Camps quinoline synthesis is in the ring contraction of macrocycles. Treatment of 9 member ring 24 with sodium hydroxide in water furnished quinolin-4-ol 25, while 26 furnishes exclusively quinolin-2-ol 27 under the same reaction conditions (no yield was given for either reaction). The reaction does not work with smaller macrocycles. The authors rationalize the difference in reactivity based upon ground state conformation differences, but do not elaborate. 

X-ray structure analysis demonstrated that the nonaromatic macrocyclc adopts a conformation which can be described as a loop conformation in which the whole macrocycle is twisted. 

Although [34]octaphyrin 80 fulfills Hiickel s rule, the II NMR spectrum indicates by the high-field shift of the methine protons that the system is nonaromatic. The X-ray structure analysis demonstrates clearly the reason for the lack of aromatic stabilization, namely the nonplanar loop conformation in which the whole macrocycle is twisted similarly to the [32]octaphyrin structure and which is also found for [36]octaphyrin and [40]decaphyrin structures (vide infra). 

According to Hiiekel s rule, turcasarin should not be aromatic, but even if the macrocycle should fulfill the (4n +2) rule for aromatic systems the lack of planarity due to the loop conformation would prevent aromatic stabilization. In fact, the existence of the loop conformation in which the whole macrocycle is twisted was demonstrated by X-ray structure analysis and NMR investigations. 

In contrast, porphyrinogens 16 (Fig. 5) possess only 16 Ti-electrons and as a consequence the delocalization over the whole macrocycle is absent. The conformations of porphyrinogens are not planar any more and can approximate to the conformations known for calix[4]arenes (vide supra). Compounds 16 (Fig. 5) may, therefore, be considered as heteroatomic calixarene derivatives, of which some have additional heteroatoms in the bridging positions [15, 28-30]. 

As in the case of the tetrameric macrocycles discussed above, compounds 17 and 18 can be considered as porphyrinogen analogues or as heteroatom-bridged heteroaromatic calix[4]arene derivatives. The two different conformations observed for 17 and 18 have analogues in compounds 16 (Fig, 5) [15, 28-30],... 

The tetrameric macrocycle of 21 has Q-symmetry and its conformation is similar to that of 18 with one opposite pair of imidazole rings in the plane of the molecule, and the other pair perpendicular to it. In 22 all five imidazole rings are almost perpendicular to the molecular plane, so that a CH2CI2 molecule can be included in the cavity of the pentamer. Unfortunately, compounds 19-23 are unstable under influence of air and moisture [33]. 

Thereby, the presence of tertiary monophosphines is critical, because both polymeric (26) and cyclic tetrameric (24 and 25) complexes can be obtained depending on the phosphine added to the reaction mixture. Furthermore, with some of the phosphines rapid decomposition and deposition of metallic silver occurs. In the macrocyclic molecules 24 and 25 a pair of silver atoms is bridged by two bis(l-imidazolyl)borate moieties, with a transannular Ag Ag distance of 8.61 A for 24 and 8.89 A for 25. The conformations of 24 and 25 are... 

The general procedure for the preparation of vanadium borates consists in heating a concentrated H2O solution of boric acid and vanadium oxide in an autoclave at 170 °C for several days [143]. Two different vanadium borate clusters 105 and 106 are obtained, one with two polyborate chains coordinated to a contorted vanadium oxide ring (105) and another one with a macrocyclic Bi8036(0H)6 ring (106). The latter ring is composed of six B306(0H) units and has a chair-like conformation (Fig. 27) [143]. 

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