Resorcin arene synthesis

Supramolecular self-assembly can be as simple as acetic acid dimerization through mutually complementary hydrogen bonds or as complex as supramolecule formation from multiple components as demonstrated by numerous examples of resorcin[4]arene and calix[4]arene capsules. One of the more interesting directions to have been taken has been the design and synthesis of self-complementary... 

Haino and co-workers have reported the synthesis of a self-assembling dimeric capsule via metal-coordination utilizing two octadentate resorcin[4]arene cavitands possessing four bipyridyl groups (13) which complex four silver cations (Ag+) in a tetrahedral fashion (Fig. 4) [46, 47]. A detailed computational study of the dimeric metallo-capsule 14 revealed a large and elaborate three-dimensional inner capsular... 

Schroder T, Sahu SN, Anselmetti D, Mattay J (2011) Supramolecular capsules derived from resorcin[4]arenes by H-bonding and metal coordination. Synthesis, characterization and single-molecule force spectroscopy. Isr J Chem 51 725... 

There has been a recent report of a very interesting, large supramolecular assembly related to the resorcin[4]arene work. The synthesis of several pyrogallol [4]arenes, 7, has been accomplished under mild conditions [32]. However, the authors report that they obtained the hexamer of C-isobutylpyrogallol[4]arene, 8, only one time out of many attempts (Figure 8). 

Mezo. A.R. Sherman. J.C. Water-soluble cavitands Synthesis of methylene-bridged resorcin[4]arenes contain-... 

Resorcinarenes (see the companion chapter by Bruno Botta) date back nearly 150 years when Baeyer discovered that the mixing of aldehydes with resorcinol in the presence of strong acid produced a red resin [2]. Over a decade later, Michael successfully determined the correct chemical composition of the product, but proposed the incorrect structure [3]. The correct structure of resorcin[4]arene (1, Scheme 9.1) was first proposed by Niederl [4], but it was almost 100 years after Baeyer s initial work that Erdtman and Hogberg obtained a definitive structure [5]. Twelve years after that, Hogberg fully documented resorcinarene synthesis,... 

One of the most recent developments in the field is the use of the self-assembled hexameric resorcin[4]arene capsules as reaction vessels or nano-reactors where new chemistry and catalysis may occurs. There are only few such examples however in the past year or so several convincing and interesting examples were reported. The most interesting to date is the terpenes synthesis from unsaturated alcohols, which seems to mimic the action of cyclase enzymes. Clearly there is more chemistry to discover with these nano-vessels. 

In order to confer the calixarenes the ability to form SAMs on metal surfaces, they have to be chemically modified to introduce chemical functions (e.g., thiol, thioether, disulfide) able of chemisorption on the surface. Reinhoudt published the synthesis of calix[4]arenes bearing four di- -decyl sulfide chains at the lower rims. The synthesis proceeds via first the alkylation of the calix[4]arene-25,26,27,28-tetrol with 10-undecen-l-yl tosylate followed by the anti-Markovnikov addition of 1-dodecanthiol in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN) (Fig. 37.11) [64]. Similarly to calix[4]arenes, resorcin[4]arenes tetrasulfides have been produced by the condensation reaction of resorcinol and 11-undecylenic aldehyde followed by the addition of 1 -dodecanthiol to the terminal double bonds of the alkyl chains using catalytic amounts of 9-BBN [63]. 

Both Resorcin[4]arenes and Quinoxalines in the Synthesis of Macrocycles... 

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