Efficient synthesis of a molecular knot by copper(I)-induced formation of the precursor followed by ruthenium(II)-catalysed ring closing metathesis

Abstract

A double-stranded helix constructed around two copper(I) centres used as templates and bearing four terminal alkenes, is converted into a trefoil knot in 74% yield by ruthenium(II)-catalysed ring closing methathesis (RCM); the cyclic alkenes can be quantitatively reduced by catalytic hydrogenation to afford the copper(I)-complexed 82-membered knotted ring.

References

1. L. F. Liu, R. E. Depew and J. C. Wang, J. Mol. Biol., 1976, 106, 439.
2. S. M. Du, B. D. Stollar and N. C. Seeman, J. Am. Chem. Soc., 1995, 117, 1194.
3. C. Liang and K. Mislow, J. Am. Chem. Soc., 1995, 117, 4201 and references therein.
4. C. O. Dietrich-Buchecker and J. P. Sauvage, Angew. Chem., Int. Ed. Engl., 1989, 28, 189; C. O. Dietrich-Buchecker, J. Guilhem, C. Pascard and J. P. Sauvage, Angew. Chem., Int. Ed. Engl., 1990, 29, 1154.
5. (a) C. O. Dietrich-Buchecker, J. P. Sauvage, J. P. Kintzinger, P. Maltese, C. Pascard and J. Guilhem, New J. Chem., 1992, 16, 931; (b) C. O. Dietrich-Buchecker, J. F. Nierengarten, J. P. Sauvage, N. Armaroli, V. Balzani and L. De Cola, J. Am. Chem. Soc., 1993, 115, 11 237; (c) M. Meyer, A. M. Albrecht-Gary, C. O. Dietrich-Buchecker and J. P. Sauvage, J. Am. Chem. Soc., 1997, 119, 4599; (d) C. O. Dietrich-Buchecker, J. P. Sauvage, N. Armaroli, P. Ceroni and V. Balzani, Angew. Chem., Int. Ed. Engl., 1996, 35, 1119.
6. C. O. Dietrich-Buchecker, J. P. Sauvage, A. De Cian and J. Fischer, J. Chem. Soc., Chem. Commun., 1994, 2231.
7. G. C. Fu and R. H. Grubbs, J. Am. Chem. Soc., 1992, 114, 5426; A. Fürstner and N. Kindler, Tetrahedron Lett., 1996, 37, 7005; B. König and C. Horn, Synlett, 1996, 1013; B. Mohr, M. Weck, J. P. Sauvage and R. H. Grubbs, Angew. Chem., Int. Ed. Engl., 1997, 36, 1308.
8. R. F. Carina, C. O. Dietrich-Buchecker and J. P. Sauvage, J. Am. Chem. Soc., 1996, 118, 9110.