Cyclophane, reduced

Template-catalyzed syntheses of peraza-cyclophanes via the cyclic oligo Schiff bases are common (Mandal et al., 1987). The reaction of a dialdehyde and a diamine to form a cyclic oligo Schiff base is usually successful, but only a few of the di or tetra Schiff bases have been reduced to the cyclic amines. Some examples of these cyclic Schiff base-forming reactions have been reported, but this subject will not be reviewed extensively because this book covers the saturated polyaza-crowns and cyclophanes. Reducing the Schiff... 

The discussion can be restricted to the first and second reduction processes that are of particular interest in this context. The shift of the bipyridinium-based process is in agreement with the catenane coconformation in which the bipyridinium unit is located inside the cavity of the macrocyclic polyether (Fig. 13.33a) because of the CT interactions established with both the electron donor units of the macrocycle, its reduction is more difficult than in the free tetracationic cyclophane. The shift of the trans-1,2-bis(4-pyridinium)ethylene-based reduction indicates that, once the bipyridinium unit is reduced, the CT interaction that stabilize the initial coconformation are destroyed and, thereby, the tetracationic cyclophane circumrotates through the cavity of the macrocyclic polyether moving the tra ,v-bis(pyridinium)ethylene unit inside, as shown by comparison of its reduction potential with that of a catenane model compound.19 The original equilibrium between the two coconformations associated with catenane 384+ is restored upon oxidation of both units back to their dicationic states. 

In ( )-49 it-electron conjugation between the two free poles is maintained through two tran.v-stilbcnc-likc bridges. As a result of this extended conjugation, the compound is red in solution, with an end absorption extending to 600 nm. This contrasts with the light-yellow color (end adsorption around 450 nm) of the hexakis adducts with a pseudo-octahedral addition pattern, in which the residual tt-electron chromophore is reduced to a benzenoid cubic cyclophane -type substructure [15,54],... 

The current-voltage curve was interpreted on the basis of the mechanism illustrated in Figure 17.15a, which is derived from the behavior of the same catenane 134+ in solution.116,117 Conformation I is the switch open state and conformation IV the switch closed state of the device. When 134+ is oxidized (+2 V), the TTF unit is ionized in state II and experiences a Coulombic repulsion inside the tetra-cationic cyclophane component, resulting in circumrotation of the crown ether and formation of conformation III (note that in solution at +2 V TTF undergoes two-electron oxidation and the dioxynaphthalene unit is also oxidized).116 When the voltage is reduced to near-zero bias, a metastable conformation IV is obtained... 

It was converted to the phthalimide via a Mitsunobu reaction, reduced to the amine, and the amine was coupled with />-nitrophenylacetic acid to give the precursor to the macrocycle. Macrocylization was done via Troger s base formation using Johnson s method, which resulted in two isomers of the amide macrocycle. These were separated and reduced to give the cyclophane host. This was the first time two diastereomers were observed in these syntheses and the separation of these diastereomers was very difficult. 

Monolayered cyclophane complexes of type 263 are also reduced by sodium bis(methoxyethoxy)aluminum hydride (Red-Al) to give (i74-diene)-(i76-cyclophane)ruthenium(0) complexes (Scheme 33). If the benzene ring of 263 (arene = benzene) is converted to the (1,3-cyclohexadiene)-ruthenium(O) derivative 271, however, when the corresponding rj6-hexa-methylbenzene is reduced with Red-Al, the product is the (if-1, 4-cyclohexadiene)ruthenium(0) complex 288. Synthesis of 271 can... 

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