Resorcinarenes - Gears of Supramolecular Chemistry

Resorcinarenes [1] are known to be versatile macrocyclic platforms for many covalent and supramolecular assemblies serving a variety of applications, e.g., ion-channel mimics [2], catalysis [3], and drug delivery [4]. Parent resorcin[4]arenes 1 (Fig. 1) form capsular complexes in solution and self-assemble at interfaces. Upon proper functionalization, resorcin[4]arenes turn into their rigidified derivatives called cavitands, such as 4 [5] and closed-shell compounds termed carcerands [6]. These compounds are capable of reversible or irreversible binding of different molecular guests.

It should be pointed out that the isolation of highly unstable cyclobuta-1,3-diene at room temperature inside a carcerand [7] is one of the most impressive examples of resorcin[4]arene applications. Regioselective acylation of resorcin[4]arenes gives tetrasubstituted compounds 2 [8]. Tetraphosphates 2a and tetraaroylates 2b were shown to form capsular dimeric complexes with cationic guests [9]. Tetrasulfonates 2c (in which Ar = 2-naphthyl) assemble into UV-polymerizable monolayers at the air/water interface [10], while distally bridged tetrasulfonates were suggested as templates for asymmetric catalysis [11]. Aminomethylated resorcin[4]arene derivatives 3 form kinetically stable complexes with halide anions [12] and small molecules, e.g., acetonitrile [13].

Life Chemicals offers highly effective custom synthesis of functionalized resorcin[4]- and [6]arene derivatives, such as the ones shown in Fig. 1. For more structural examples, see the relevant references.

Please, contact us at marketing@lifechemicals.com for any additional information and price quotations.

For further reading, please, refer to our MedChem blog dedicated to Building Blocks and Custom synthesis

Figure 1. Representative structures of the resorcinarenes, available upon request from Life Chemicals.

References:

1. (a) Sliwa, W.; Kozlowski, C. Calixarenes and resorcinarenes. 2009, Wiley VCH, Weinheim. (b) Timmerman, P.; Verboom, W.; Reinhoudt, D. N. Tetrahedron 1996, 52, 2663–2704.
2. Wright, A. J.; Matthews, S. E.; Fischer, W. B.; Beer, P. D. Chem. Eur. J. 2001, 7, 3474–3481.
3. Zhang, Q.; Catti, L.; Tiefenbacher, K. Acc. Chem. Res. 2018, 51, 2107–2114.
4. Shumatbaeva, A. M.; Morozova, J. E.; Syakaev, V. V. et al. Colloids Surf. A Physicochem. Eng. 2020, 589, 124453.
5. Körner, S. K.; Tucci, F. C.; Rudkevich, D. M.; Heinz, T.; Rebek, J. Jr. Chem. Eur. J. 2000, 6, 187–195.
6. Cram, D. J.; Cram, J. M. Container Molecules and Their Guests 1997, The Royal Society of Chemistry, London.
7.  Cram, D. J.; Tanner, M. E.; Thomas, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1024.
8. (a) Kalchenko, V. I.; Rudkevich, D. M.; Shivanyuk, A. N.; Pirozhenko, V. V.; Tsymbal, I. F.; Markovsky, L. N. Zh. Obshch. Khim. 1994, 64, 731–742; Russ. J. Gen. Chem. 1994, 64, 663–672. (b) Lukin, O.; Pirozhenko, V. V.; Shivanyuk, A. N. Tetrahedron Lett. 1995, 36, 7725–7728. (c) Shivanyuk, A.; Paulus, E. F.; Böhmer, V.; Vogt, W. J. Org. Chem. 1998, 63, 6448–6449.
9. (a) Shivanyuk, A.; Paulus, E. F.; Böhmer, V. Angew. Chem. Int. Ed. 1999, 38, 2906–2909. (b) Shivanyuk, A. Tetrahedron 2005, 61, 349–352
10.  Semenok, D.; Kletskov, A.; Burilov, V.; Luchkin, S.; Potkin, V.; Lukin, O. Mater. Today Commun. 2020, 25, 101334.
11. Arnott, G.; Hunter, R. Tetrahedron 2006, 62, 992–1000.
12. Shivanyuk, A.; Spaniol, T. P.; Rissanen, K.; Kolehmainen, E.; Böhmer, V. Angew. Chem., Int. Ed. 2000, 39, 3497–3500.
13.  Falábu, D.; Shivanyuk, A.; Nissinen, M.; Rissanen, K. Org. Lett. 2002, 4, 3019–3022.