Synlett 2016; 27(02): 177-180
DOI: 10.1055/s-0035-1560221
synpacts
© Georg Thieme Verlag Stuttgart · New York

Small Is (also) Beautiful: Dynamic Covalent Self-Assembly of Cryptates

Max von Delius*
Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander University Erlangen-Nuremberg (FAU), Henkestr. 42, 91054 Erlangen, Germany   Email: max.vondelius@fau.de
› Author Affiliations
Further Information

Publication History

Received: 06 August 2015

Accepted: 14 August 2015

Publication Date:
03 September 2015 (online)


Abstract

Cryptands can be seen as the smallest three-dimensional molecular cages still capable of accommodating (ionic) guests. We have recently realized the first dynamic covalent self-assembly of a monometallic cryptate, whose template synthesis and unique structure crucially rest on orthoester bridgeheads [Nat. Commun. 2015, 6, 7129]. In this Synpacts article, I discuss selected aspects that led to this discovery and I attempt to put the study into the context of recent trends in the self-assembly of larger molecular cages.

1 Introduction

2 Dynamic Covalent Self-Assembly of Orthoester Cryptates

3 From Covalent to Metallosupramolecular to Dynamic Covalent Synthesis

4 Orthoester Cryptates as Tiny Self-Assembled Cages

5 Conclusions

 
  • References and Notes

  • 1 Supramolecular Chemistry. Steed JW, Gale PA. Wiley-VCH; Weinheim: 2012
    • 2a Pedersen CJ. J. Am. Chem. Soc. 1967; 89: 7017
    • 2b Dietrich B, Lehn JM, Sauvage JP. Tetrahedron Lett. 1969; 10: 2885
    • 2c Ogoshi T, Kanai S, Fujinami S, Yamagishi T.-a, Nakamoto Y. J. Am. Chem. Soc. 2008; 130: 5022
    • 2d Lee S, Chen C.-H, Flood AH. Nat. Chem. 2013; 5: 704
  • 3 Lehn J.-M. Angew. Chem. Int. Ed. 2015; 54: 3276
    • 4a Corbett PT, Leclaire J, Vial L, West KR, Wietor J.-L, Sanders JK. M, Otto S. Chem. Rev. 2006; 106: 3652
    • 4b Jin Y, Wang Q, Taynton P, Zhang W. Acc. Chem. Res. 2014; 47: 1575
  • 5 Brachvogel R.-C, von Delius M. Chem. Sci. 2015; 6: 1399
  • 7 A major limitation of orthoester exchange as a tool for DCC is its incompatibility with water. During acid-catalyzed exchange reactions, water has to be excluded to avoid hydrolysis to esters.
    • 8a Ludlow RF, Otto S. Chem. Soc. Rev. 2008; 37: 101
    • 8b Mattia E, Otto S. Nat. Nanotech. 2015; 10: 111
  • 9 Slater AG, Cooper AI. Science 2015; 348 : in press; DOI: 10.1126/science.aaa8075
  • 10 Brachvogel R.-C, Hampel F, von Delius M. Nat. Commun. 2015; 6: 7129
  • 11 Gokel GW In Crown Ethers and Cryptands. Royal Society of Chemistry; Cambridge: 1991
  • 12 Brachvogel R.-C, Maid H, von Delius M. Int. J. Mol. Sci. 2015; 16: 20641
  • 13 Krossing I, Raabe I. Angew. Chem. Int. Ed. 2004; 43: 2066
    • 14a Coxon AC, Stoddart JF. J. Chem. Soc., Perkin Trans. 1 1977; 767
    • 14b Parsons DG. J. Chem. Soc., Perkin Trans. 1 1978; 451
    • 15a Saalfrank RW, Dresel A, Seitz V, Trummer S, Hampel F, Teichert M, Stalke D, Stadler C, Daub J, Schünemann V, Trautwein AX. Chem. Eur. J. 1997; 3: 2058
    • 15b Saalfrank RW, Maid H, Scheurer A. Angew. Chem. Int. Ed. 2008; 47: 8794
    • 16a Cram DJ. Science 1983; 219: 1177
    • 16b Harris K, Fujita D, Fujita M. Chem. Commun. 2013; 49: 6703
    • 16c Han M, Engelhard DM, Clever GH. Chem. Soc. Rev. 2014; 43: 1848
    • 16d Brown CJ, Toste FD, Bergman RG, Raymond KN. Chem. Rev. 2015; 115: 3012
    • 16e Smulders MM. J, Riddell IA, Browne C, Nitschke JR. Chem. Soc. Rev. 2013; 42: 1728
    • 16f Zhang G, Mastalerz M. Chem. Soc. Rev. 2014; 43: 1934
    • 17a Chichak KS, Cantrill SJ, Pease AR, Chiu S.-H, Cave GW. V, Atwood JL, Stoddart JF. Science 2004; 304: 1308
    • 17b Ponnuswamy N, Cougnon FB. L, Clough JM, Pantoş GD, Sanders JK. M. Science 2012; 338: 783
    • 17c Ayme J.-F, Beves JE, Leigh DA, McBurney RT, Rissanen K, Schultz D. Nat. Chem. 2012; 4: 15
    • 18a Fujita D, Suzuki K, Sato S, Yagi-Utsumi M, Yamaguchi Y, Mizuno N, Kumasaka T, Takata M, Noda M, Uchiyama S, Kato K, Fujita M. Nat. Commun. 2012; 3: 1093
    • 18b Zhang G, Presly O, White F, Oppel IM, Mastalerz M. Angew. Chem. Int. Ed. 2014; 53: 1516