The synthesis and solubilization of amide macrocycles via rotaxane formation

Journal of the American Chemical Society

Volumn 118, Issue 43, 1996, Pages 10662-10663

  Johnston, Andrew G ^a   Leigh, David A ^a   Murphy, Aden ^a   Smart, John P ^a   Deegan, Michael D ^b  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

^b British Gas Exploration and Production   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

MACROCYCLIC COMPOUND;

ARTICLE; NUCLEAR MAGNETIC RESONANCE; SOLUBILIZATION; TECHNIQUE;

EID: 0029849783     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962046r     Document Type: Article

References (28)

1. A classic example is Cram's isolation of cyclobutadiene where a problematic property of the hydrocarbon (its high chemical reactivity) is overcome by insulating it from other reactive species inside a carcerand [Cram, D. J.; Tanner, M. E.; Thomas, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1024-1027]. Examples involving topologically nontrivial compounds include the Stoddart synthesis of a [3]catenane which is more efficient than that of its central ring component on its own because stabilizing interactions during catenation overcome the kinetic barrier to macrocyclization [Amabilino, D. B.; Ashton, P. R.; Brown, C. L.; Córdova, E.; Godinez, L. A.; Goodnow, T. T.; Kaifer, A. E.; Newton, S. P.; Pietraszkiewicz, M.; Philp, D.; Raymo, F. M.; Reder, A. S.; Rutland, M. T.; Slawin, A. M. Z.; Spencer, N.; Stoddart, J. F.; Williams, D. J. J. Am. Chem. Soc. 1995, 117, 1271-1293]. Catenanes are also intermediates in some DNA replication processes [Bates, A. D.; Maxwell, A. DNA Topology; Oxford university Press: New York, 1993].
2. A classic example is Cram's isolation of cyclobutadiene where a problematic property of the hydrocarbon (its high chemical reactivity) is overcome by insulating it from other reactive species inside a carcerand [Cram, D. J.; Tanner, M. E.; Thomas, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1024-1027]. Examples involving topologically nontrivial compounds include the Stoddart synthesis of a [3]catenane which is more efficient than that of its central ring component on its own because stabilizing interactions during catenation overcome the kinetic barrier to macrocyclization [Amabilino, D. B.; Ashton, P. R.; Brown, C. L.; Córdova, E.; Godinez, L. A.; Goodnow, T. T.; Kaifer, A. E.; Newton, S. P.; Pietraszkiewicz, M.; Philp, D.; Raymo, F. M.; Reder, A. S.; Rutland, M. T.; Slawin, A. M. Z.; Spencer, N.; Stoddart, J. F.; Williams, D. J. J. Am. Chem. Soc. 1995, 117, 1271-1293]. Catenanes are also intermediates in some DNA replication processes [Bates, A. D.; Maxwell, A. DNA Topology; Oxford university Press: New York, 1993].
3. A classic example is Cram's isolation of cyclobutadiene where a problematic property of the hydrocarbon (its high chemical reactivity) is overcome by insulating it from other reactive species inside a carcerand [Cram, D. J.; Tanner, M. E.; Thomas, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1024-1027]. Examples involving topologically nontrivial compounds include the Stoddart synthesis of a [3]catenane which is more efficient than that of its central ring component on its own because stabilizing interactions during catenation overcome the kinetic barrier to macrocyclization [Amabilino, D. B.; Ashton, P. R.; Brown, C. L.; Córdova, E.; Godinez, L. A.; Goodnow, T. T.; Kaifer, A. E.; Newton, S. P.; Pietraszkiewicz, M.; Philp, D.; Raymo, F. M.; Reder, A. S.; Rutland, M. T.; Slawin, A. M. Z.; Spencer, N.; Stoddart, J. F.; Williams, D. J. J. Am. Chem. Soc. 1995, 117, 1271-1293]. Catenanes are also intermediates in some DNA replication processes [Bates, A. D.; Maxwell, A. DNA Topology; Oxford university Press: New York, 1993].
4. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
5. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
6. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
7. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
8. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
9. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
10. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
11. The only other examples of rotaxane syntheses where the macrocycle is cyclized around the thread are based upon the π-electron rich/π-electron deficient system developed by Stoddart [Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725-2828], although Sauvage has applied similar "clipping" strategies extensively in catenane synthesis [Dietrich-Buchecker, C. O.; Sauvage, J. P. Chem. Rev. 1987, 87, 795-810 and Sauvage, J. P. Ace. Chem. Res. 1990, 23, 319-327]. Vögtle has recently reported the synthesis of amide-based rotaxanes via a "threading" strategy. See: Vögtle, F.; Handel, M.; Meier, S.; Ottens-Hildebrandt, S.; Ott, F.; Schmidt, T. Liebigs Ann. Chem. 1995, 739-743. Vögtle, F.; Jäger, R.; Händel, M.; Ottens-Hildebrandt, S.; Schmidt, W. Synthesis 1996, 353-356. Vögtle, F.; Jäger, R., Händel, M.; Ottens-Hildebrandt, S. Pure Appl. Chem. 1996, 68, 225-232. Vögtle, F.; Händel, M.; Jäger, R.; Meier, S.; Harder, G. Chem. Eur. J. 1996, 2, 640-643. Jäger, R.; Händel, M.; Harren, J.; Rissanen, K.; Vögtie, F. Liebigs Ann. Chem. 1996, 1201-1207.
12. Degradabie catenanes and rotaxanes date back to some of the earliest examples of catenane and rotaxane synthesis [Wasserman, E. J. Am. Chem. Soc. 1960, 82, 4433-4434 and Harrison, I. T.; Harrison, S. J. Am. Chem. Soc. 1967, 89, 5723-5724]. The Birmingham group has recently described their utility in the templated synthesis of a "molecular square", see: Raymo, F. M.; Stoddart, J. F. Pure Appl. Chem. 1996, 68, 313-322. Asakawa, M.; Ashton, P. R.; Menzer, S.; Raymo, F. M.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1996, 2, 877-893.
13. Degradabie catenanes and rotaxanes date back to some of the earliest examples of catenane and rotaxane synthesis [Wasserman, E. J. Am. Chem. Soc. 1960, 82, 4433-4434 and Harrison, I. T.; Harrison, S. J. Am. Chem. Soc. 1967, 89, 5723-5724]. The Birmingham group has recently described their utility in the templated synthesis of a "molecular square", see: Raymo, F. M.; Stoddart, J. F. Pure Appl. Chem. 1996, 68, 313-322. Asakawa, M.; Ashton, P. R.; Menzer, S.; Raymo, F. M.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1996, 2, 877-893.
14. Degradabie catenanes and rotaxanes date back to some of the earliest examples of catenane and rotaxane synthesis [Wasserman, E. J. Am. Chem. Soc. 1960, 82, 4433-4434 and Harrison, I. T.; Harrison, S. J. Am. Chem. Soc. 1967, 89, 5723-5724]. The Birmingham group has recently described their utility in the templated synthesis of a "molecular square", see: Raymo, F. M.; Stoddart, J. F. Pure Appl. Chem. 1996, 68, 313-322. Asakawa, M.; Ashton, P. R.; Menzer, S.; Raymo, F. M.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1996, 2, 877-893.
15. Degradabie catenanes and rotaxanes date back to some of the earliest examples of catenane and rotaxane synthesis [Wasserman, E. J. Am. Chem. Soc. 1960, 82, 4433-4434 and Harrison, I. T.; Harrison, S. J. Am. Chem. Soc. 1967, 89, 5723-5724]. The Birmingham group has recently described their utility in the templated synthesis of a "molecular square", see: Raymo, F. M.; Stoddart, J. F. Pure Appl. Chem. 1996, 68, 313-322. Asakawa, M.; Ashton, P. R.; Menzer, S.; Raymo, F. M.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1996, 2, 877-893.
16. Johnston, A. G.; Leigh, D. A.; Pritchard, R. J.; Deegan, M. D. Angew. Chem., Int. Ed. Engl. 1995, 34, 1209-1212.
17. Yang, H. H. Aromatic High-Strength Fibers; John Wiley & Sons: New York, 1989.
18. Protein Folding: Creighton, T. E., Ed.; Freeman: New York, 1992.
19. 3N, THF; 56% overall yield.
20. The reaction reaches a virtual end point after several equivalents of acid chloride and bisamine are added, probably because of the buildup of the concentration of amide, amine, and ammonium species which can compete for and disrupt the hydrogen bonding necessary for the rotaxane assembly mechanism. Filtration and washing of the reaction mixture can be used to increase the yield of [2]rotaxane if necessary.
21. -1 at 298 K) reflecting an increased degree of molecular rearrangement that must happen in order for shuttling to occur.
22. Solvent-dependent translational isomerism has been observed in (a) amphiphilic benzylic amide catenanes [Leigh, D. A.; Moody, K.; Smart, J. P.; Watson, K. J.; Slawin, A. M. Z. Angew. Chem., Int. Ed. Engl. 1996, 35, 306-310] and (b) some of the Stoddart catenanes [Ashton, P. R.; Blower, M.; Philp, D.; Spencer, N.; Stoddart, J. F.; Tolley, M. S.; Ballardini, R.; Ciano, M.; Balzani, V.; Gandolfi, M. T.; Prodi, L.; McLean, C. H. New J. Chem. 1993, 17, 689-695].
23. Solvent-dependent translational isomerism has been observed in (a) amphiphilic benzylic amide catenanes [Leigh, D. A.; Moody, K.; Smart, J. P.; Watson, K. J.; Slawin, A. M. Z. Angew. Chem., Int. Ed. Engl. 1996, 35, 306-310] and (b) some of the Stoddart catenanes [Ashton, P. R.; Blower, M.; Philp, D.; Spencer, N.; Stoddart, J. F.; Tolley, M. S.; Ballardini, R.; Ciano, M.; Balzani, V.; Gandolfi, M. T.; Prodi, L.; McLean, C. H. New J. Chem. 1993, 17, 689-695].
24. Johnston, A. G.; Leigh, D. A.; Nezhat, L.; Smart, J. P.; Deegan, M. D. Angew, Chem., Int. Ed. Engl. 1995, 34, 1212-1216. The (n + n) notation indicates the number of reactant molecules used to form each interlocked component of the product.
25. 2 confers a symmetrical electron density around the O=C=O axis.
26. 2 in nonpolar solvents as well as thin films.
27. 2 binding is primarily within the cavity of 1, however, since "nondesigned" exocyclic binding which is not normally a significant process in solution can play an important role in gas-solid interface host-guest systems [Grate, J. W.; Patrash, S. J.; Abraham, M. H.; Du, C. M. Anal. Chem. 1996, 68, 913-917].
28. Gibson, H. W.; Liu, S.; Lecavalier, P.; Wu, C.; Shen, Y. X. J. Am. Chem. Soc. 1995, 117, 852-874 and references therein.