Coronand Crown ether

The ion-pair dissociation of ambident alkali enolates, which results in increasing 0/C alkylation ratios, can be promoted not only by dissociating solvents but also by specific cation solvation. In the latter case, EPD solvents cf. DMF and DMSO in Table 5-22b) or macro(poly)cyclic ligands such as coronands ( crown ethers ) or cryptands are used [376, 377, 660]. For example, the alkylation of sodium y9-naphtholate with (bromomethyl)benzene or iodomethane in the presence of benzo[18]crown-6 gives high O/C alkylation ratios when tetrahydrofuran or benzene are the solvents [660]. In dissociating solvents such as A,A-dimethylformamide or acetonitrile, however, so far no... 

Podates AcycHc analogues of crown ethers /coronands and cryptands (podands, eg, (11) (30) are also capable of forming inclusion compounds (podates) with cations and uncharged organic molecules, the latter being endowed with a hydrogen bond fiinctionahty. Podates normally are less stable than coronates and cryptates but have favorable kinetics. 

Crown ether This term would refer specifically to coronands (see above) containing only oxygen heteroatoms in the ring. 

As stated above, systematic names of macrocyclic host molecules were absurdly complicated for routine discussions [22]. Therefore Vogtle proposed the name coronand for crown ethers, and that of coronates for their complexes while cryptand complexes were called cryptates . The corresponding noncyclic analogues are podands such as 64 [23] and podates, respectively. The cumbersome name podando-coronands (and correspondingly podando-coronates ) was proposed for lariat ethers [24] having at least one sidearm like 65. Examples of hemispherands 66 [25], cavitands 25 [26] and those of some other hosts are discussed in Chapter 7 in some detail, whilst the exceptional stability of fragile guests 4 [2a] and 67 [27] in the hemicarcerand 5 cavity are discussed in Chapters 1 and Section 7.3. 

Multidentate ligands, both acyclic and cyclic, are now abundant and herein the nomenclature used will follow that recently proposed by Vogtle and Weber.33 Coronands are taken to mean macromonocyclic compounds having any heteroatoms present as potential donors, with crown ethers being reserved for compounds of the same type having only oxygen atoms present as... 

Alkali Metals and Group IIA Metals 23.5.1 Crown Ethers and Coronands... 

Macropolycyclic ligands containing intramolecular cavities of a three-dimensional nature are referred to as cryptands. The bicyclic cryptands (73) exist in three conformations with respect to the terminal nitrogen atoms, exo-exo, endo-exo and endo-endo 6 these forms can rapidly interconvert via nitrogen inversion but only the endo-endo form has been found in the crystal structures of a variety of complexes372 and for the free ligand ([2.2.2], 73, m = n = / = l).449 In their complexes with alkali and alkaline earth cations, the cryptands exhibit an enhanced stability over the crown ethers and coronands dufe to the macrobicyclic, or cryptate, effect.33 202... 

An additional nuance in the nomenclature of these compounds concerns their complexes. The open-chained compounds are often referred to as podands and their complexes as podates. The cyclic ethers may also be called coronands and their complexes are therefore coronates. Complexed cryptands are cryptates. The even more complicated structures known as spherands, cavitands, or carcerands are called spherates, cavitates, or carcerates, respectively, when complexed. The combination of a macrocycle (crown ether or coro-nand) and a sidechain (podand) is typically called a lariat ether. 

Vogtle has suggested that synthetic ionophores be classified as follows (21) cor-onands are macromonocyclic compounds with any heteroatoms cryptands are bi- and polymacrocyclic ligands with any heteroatoms and podands are acyclic coronand and cryptand analogs. The term crown ether is reserved for coronands with only oxygens as heteroatoms. Such a classification will be used hereafter. 

Cation complexes of cryptands were called cryptates and those of spherands, spherates. The name coronand was suggested for crown ethers and their complexes would therefore be coronates <1980ICAL45>. The latter nomenclature has proved to be acceptable to the community but it has not been universally adopted. A reasonable and systematic approach, based on principles of polymer nomenclature, has appeared but has not found wide acceptance <1984JCI266>. 

Other anions (X = Br , I , HO , CH3O ) also exhibit enhanced nucleophilic reactivity in crown-ether mediated reactions of K X [357, 358], Montanari et al. [653] compared the effects of phosphonium salts, coronands, and cryptands on the Sn2 reaction of -octylmethanesulfonate with various nucleophiles in chlorobenzene. 

The late 60 s and the early 70 s saw the advent of the first artificial molecules where these concepts were fully utilised, the crown ethers and their sequels the cryptands. Crown ethers or coronands are hetero-cyclic structures where the hetero-atoms are separated with C2-units cryptands are bicyclic analogues... 

Crown ethers, stability and reactivity of complexes 80APO(17)279. Cryptands and coronands, complexes with anions 83BSF(2)367. 

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