Amines macrobicyclic

Alder and Sessions have reported that reductive cleavage of hydrazinium dications is a useful approach to macrobicyclic amines of the type developed by Park and Sim-mons , but the method does not appear to have been successfully applied to any cryptand syntheses. 

The in-out bicyclic amines prepared by Simmons and Park bear a remarkable semblance to the cryptands but lack the binding sites in the bridges. As a result, these molecules interact with electrophiles in a fashion similar to other tertiary amines and generally do not exhibit strong interactions with alkali or alkaline earth metal ions. The in-out bicyclic amines are prepared by reaction of the appropriate acid chlorides and amines in two stages to yield the macrobicyclic amine after reduction of the amidic linkages. A typical amine is shown above as compound 18. 

Park CH, Simmons HE (1968) Macrobicyclic amines. III. Encapsulation of halide ions by in, in-1,(k + 2)-diazabicyclo[k.l.m]alkane-ammonium ions. J Am Chem Soc 90 2431-2432... 

Kinetically inert low-spin cobalt (III) clathrochelates are reversibly reduced by accepting one electron to yield kinetically labile cobalt(II) complexes. In the case of the usual amines (for instance, ammonia), the reduction is, as a rule, accompanied by irreversible decay of the amine cobalt complex. This reaction is slower for chelating amines macrocyclic and especially macrobicyclic amines produce complexes with cobalt(II) ion that are stable over a long time. This fact facilitates the study of the reduction of cobalt(III) complexes to cobalt(II) ones. In most cases, the reactions of macrobicyclic ligands do not interfere with this process. 

The simple but rather useful molecular mechanics calculations were applied to both electron transfer kinetics and reduction potentials for a wide range of hexamine cobalt(III/II) complexes with primary, secondary, tertiary, and macrobicyclic amine ligands [237]. The redox potentials of the Co +/2+ couples varied from... 

Shortly after their first report of all-oxygen bridged cryptands, Dietrich, Lehn and Sauvage reported incorporation of sulfur in the strands. The experimental methods used were essentially similar to those applied in the syntheses of the parent cryptands. As in previous cases, a diacyl chloride was condensed with a diamine under high dilution conditions. In this case, however, the diamine contained sulfur atoms rather than oxygen. The synthesis of compound 5 was accomplished in two stages as illustrated below in Eq. (8.3). The first cyclization step affords the macrocyclic amine in 55% yield. The macrobicyclic product (5) is formed in 25% yield from the monocyclic diamine and the acid chloride. 

Recently considerable attention has been directed at anion binding ligands. Macrobicyclic 27 29) and macrotricyclic amines 30,31) were topologically designed to host anions such as spherical Cl-, linear Nf 32). These anion substrates are incorporated into macrocyclic cavities lined with appropriate anion-binding sites capable of forming hydrogen bonds like those of protonated amines (see /, below). 

The remarkable physical properties exhibited by the divalent macrobicyclic cage complex [Co(sep)]2+ (29) are unparalleled in Co chemistry.219 The complex, characterized structurally, is inert to ligand substitution in its optically pure form and resists racemization in stark contrast to its [Co(en)3]2+ parent. The encapsulating nature of the sep ligand ensures outer sphere electron transfer in all redox reactions. For example, unlike most divalent Co amines, the aerial oxidation of (29) does not involve a peroxo-bound intermediate. 

Smaller macrobicycles and macrotricycles bearing less that six N-donors are also known. These ligands comprise tertiary or secondary amines and are derived from insertion of one or more straps between pairs of potentially bridgehead N-donors contained within a small ring macrocycle, and in this sense they may be considered analogs of the well-known azacryptands. The inability to offer six N-donors, and the presence of tertiary amines in these ligands leads to the preference for divalent over trivalent Co. 

Sargeson and co-workers have reported the use of [Pt(en)3]4+ in template reactions to produce the platinum(IV) complexes of the macrobicyclic ligands sep and (N02)2sar (170).477 These reactions are analogous to those that occur around cobalt(III). However, in contrast to the [Co((N02)2sar)]3+ system, reduction of the pendant dinitro groups did not yield amines, but hydroxyamine groups.478... 

Severin and coworkers reported (146) the reaction of tris(2-aminoethyl)amine and 4-formylphenylboronic acid with penta-erythritol to give, via multicomponent assembly, the boronic acid based macrobicyclic cage 35 (Fig. 25). The cage has the form of an ellipsoid with a diameter of 20.5 A and binds two Cud) ions in a fashion similar to the smaller tren-based cryptands. The reversible formation of boronic esters has also been employed to build other hollow structures such as nanotubes (147) and porous covalent organic frameworks (148,149). 

The most dramatic rate retardations of proton transfers have been observed when the acidic or basic site is contained within a molecular cavity. The first kinetic and equilibrium studies of the protonation of such a basic site were made with large ring bicyclic diamines [72] (Simmons and Park, 1968 Park and Simmons, 1968a). It was also observed (Park and Simmons, 1968b) that chloride ion could be trapped inside the diprotonated amines. The binding of metal ions and small molecules by macrocyclic compounds is now a well-known phenomenon (Pedersen, 1967, 1978 Lehn, 1978). In the first studies of proton encapsulation, equilibrium and kinetic measurements were made with several macrobicyclic diamines [72] using an nmr technique. 

Amides, macrobicyclic, reduction of, 54, 89 Amine oxides, anhydrous, 50,... 

A number of other acyclic ligand systems have been developed that use tris(aminoethyl)amine (tren) as a central unit (for macrobicycles... 

The synthetic routes may often involve template directed condensations, a widely used reaction being the (carbonyl + amine) to imine condensation that efficiently leads to a variety of Schiff-base macrocycles [2.58-2.60, A.7, A.14], macrobicyclic cryptands [2.61-2.63] and lacunar cyclidene ligands [2.60, 2.64]. 

Numerous dinucleating macrocyclic and macrobicyclic ligands have been synthesized, in particular by the versatile amine + carbonyl — imine reaction they form dinuclear metal complexes as well as cascade complexes with bridging groups [2.58-2.63, 3.24-3.27, 4.1-4.4], for instance in dicobalt complexes that are oxygen carriers [3.26]. 

A vast range of Schiff base macrocycles and macrobicycles exist and have been of great importance in macrocyclic coordination chemistry, particularly of the transition metals, from the very beginning of supramolecular chemistry. The key Schiff base condensation reaction involves simply the reaction of an amine with an aldehyde to eliminate (condense) water and give an imine. If desired, the product may be reduced (e.g. with NaBH4) to give an amine or a secondary amine-based macrocycle (Scheme 3.21). 

Macrobicyclic cascade cryptands have also been prepared such as the series of bis(tren) derived (tren = tris(2-aminoethyl) amine, see Section 4.4.3) compounds 5.9. The di-nickel(II) and di-copper(II) complexes of the cages with various spacers all bind a metal cation into each tren unit. These metal... 

Drago and Elias s idea [46] to employ tridentate amines for protection of one of the two triangular bases of hexacoordinate d-metal ions coordination polyhedron (in case the latter act as capping agents) from polymerization has successfully been developed by P. Chaudhuri and K. Wieghardt for the synthesis of linear homo-and heterotrinuclear macrobicyclic complexes with tris-dioximate bridging ligands. 

Adamantanetriontrioxime may be regarded as an analog of tripodal amines in the synthesis of macrobicyclic Schiff bases and is promising in the formation of rigid clathrochelates with expanded cavity (Scheme 146). 

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