Chiral recognition of dicarboxylate anions by sapphyrin-based receptors

Journal of the American Chemical Society

Volumn 119, Issue 40, 1997, Pages 9385-9392

  Sessler, Jonathan L ^a   Andrievsky, Andrei ^a   Král, Vladimír ^a   Lynch, Vincent ^a  

^a The University of Texas at Austin   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DICARBOXYLIC ACID; DIMER; PORPHYRIN DERIVATIVE; RECEPTOR; SAPPHYRIN DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; BINDING AFFINITY; MASS SPECTROMETRY; MOLECULAR RECOGNITION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RECEPTOR AFFINITY; SYNTHESIS;

EID: 0030730747     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971614f     Document Type: Article

References (94)

1. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
2. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
3. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
4. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
5. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
6. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
7. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
8. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
9. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
10. (a) A first book, entirely dedicated to the problems of molecular recognition of anions, is due to appear soon: Bianchi, A.; Bowman-James, K.; Garcia-España, E., Eds.: The Supramolecular Chemistry of Anions; VCH: Weinheim, 1997, in press. For other reviews, see: (b) Lehn, J.-M.; Supramolecular Chemistry; VCH: Weinheim, 1995. Dietrich, B. Pure. Appl. Chem. 1993, 65, 1457-1464. Kimura, E. Top. Curr. Chem. 1985, 128, 113-141. (e) Schmidtchen, F. P.; Gleich, A.; Schummer, A. Pure. Appl. Chem. 1989, 61, 1535-1546. (f) Beer, P. D. Chem. Commun. 1996, 689-696. (g) Atwood, J. L.; Holman, K. T.; Steed, J. W. Chem. Commun. 1996, 1401-1407. (h) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S.; Bruening, R. L. Chem. Rev. 1995, 95, 2529-2586. Hannon, C. L.; Anslyn, E. V. Bioorganic Frontiers: Springer Verlag: Berlin, 1993; Vol. 3, pp 143-256. (j) For an excellent collection of reviews on molecular recognition, see: Atwood, J. L.; Davies, J. E. D.; Macnicol, D. D.; Vögtle, F., Eds. Comprehensive Supramolecular Chemistry; Elsevier: Exeter, 1996.
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17. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
18. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
19. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
20. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
21. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
22. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
23. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
24. Depending on the structural characteristics and microenvironment, the carboxylate groups, either individually or jointly, can be in their neutral (protonated) or anionic (deprotonated) forms. This complicates the problem of dicarboxylate/dicarboxylic acid recognition. In this paper we have elected to concentrate on dicarboxylate dianion binding only. For a few examples of receptors for neutral dicarboxylic acids, see: (a) Rebek, J., Jr.; Nemeth, D.; Ballester, P.; Lin, F.-T. J. Am. Chem. Soc. 1987, 109, 3474-3475. (b) Tanaka, Y.; Kato, Y.; Aoyama, Y. J. Am. Chem. Soc. 1990, 112. 2807-2808. Prevot-Halter, I.; Smith, T. J.; Weiss, J. J. Org. Chem. 1997, 62, 2186-2192. Raposo, C.; Luengo, A.; Almaraz, M.; Martin, M.; Mussons, L.; Caballero, C.; Moran, J. R. Tetrahedron 1996, 52, 12323-12332 and references therein. (e) Goodman, M. S.; Hamilton, A. D.; Weiss, J. J. Am. Chem. Soc. 1995, 117, 8447-8455 and references therein. (f) Owens, L.; Thilgen, C.; Diederich, F.; Knobler, C. B. Helv. Chim. Acta 1993, 76, 2757-2774 and references therein. (g) Alcazar, V.; Moran, J. R.; Diederich, F. Isr. J. Chem. 1992, 32, 69-77. (h) Garcia-Tellado, F.; Goswami, S.; Geib, S. J.; Hamilton, A. D. J. Am. Chem. Soc. 1990, 112, 7393-7394.
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41. (a) For an excellent review concerning enantiosetective molecular recognition, see: Webb, T. H.; Wilcox, C. S. Chem. Soc. Rev. 1993, 383-395. (b) Partial chiral resolution of dicarboxylic acids, but not dicarboxylate anions, was achieved using chiral spirobifluorene and helicopodand skeletons functionalized with amidopyridine binding sites: Alcazar, V.; Diederich, F. Angew. Chem. Int. Ed. Engl 1992, 31, 1521-1523. See also ref 5f. A chiral binaphthyl spacer placed between two (acylamino)pyridine binding moieties has also allowed a level of enantioselective differentiation in the case of tartaric acid. See ref 10a and Garcia-Tellado, F.; Albert, J.; Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1991, 1761-1763. Enantioselective complexation of N-Cbz-L-glutamic acid was observed using cage-like receptors: Pieters, R. J.; Diederich. F. Chem. Commun. 1996, 2255-2256. (e) The inherent right-handed helicity of poly(L-glutamic acid) was recently recognized using a chiral metalloporphyrin receptor: Konishi, K.; Kimata, S.; Yoshida, K.; Tanaka, M.; Aida, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2823-2825.
42. (a) For an excellent review concerning enantiosetective molecular recognition, see: Webb, T. H.; Wilcox, C. S. Chem. Soc. Rev. 1993, 383-395. (b) Partial chiral resolution of dicarboxylic acids, but not dicarboxylate anions, was achieved using chiral spirobifluorene and helicopodand skeletons functionalized with amidopyridine binding sites: Alcazar, V.; Diederich, F. Angew. Chem. Int. Ed. Engl 1992, 31, 1521-1523. See also ref 5f. A chiral binaphthyl spacer placed between two (acylamino)pyridine binding moieties has also allowed a level of enantioselective differentiation in the case of tartaric acid. See ref 10a and Garcia-Tellado, F.; Albert, J.; Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1991, 1761-1763. Enantioselective complexation of N-Cbz-L-glutamic acid was observed using cage-like receptors: Pieters, R. J.; Diederich. F. Chem. Commun. 1996, 2255-2256. (e) The inherent right-handed helicity of poly(L-glutamic acid) was recently recognized using a chiral metalloporphyrin receptor: Konishi, K.; Kimata, S.; Yoshida, K.; Tanaka, M.; Aida, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2823-2825.
43. (a) For an excellent review concerning enantiosetective molecular recognition, see: Webb, T. H.; Wilcox, C. S. Chem. Soc. Rev. 1993, 383-395. (b) Partial chiral resolution of dicarboxylic acids, but not dicarboxylate anions, was achieved using chiral spirobifluorene and helicopodand skeletons functionalized with amidopyridine binding sites: Alcazar, V.; Diederich, F. Angew. Chem. Int. Ed. Engl 1992, 31, 1521-1523. See also ref 5f. A chiral binaphthyl spacer placed between two (acylamino)pyridine binding moieties has also allowed a level of enantioselective differentiation in the case of tartaric acid. See ref 10a and Garcia-Tellado, F.; Albert, J.; Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1991, 1761-1763. Enantioselective complexation of N-Cbz-L-glutamic acid was observed using cage-like receptors: Pieters, R. J.; Diederich. F. Chem. Commun. 1996, 2255-2256. (e) The inherent right-handed helicity of poly(L-glutamic acid) was recently recognized using a chiral metalloporphyrin receptor: Konishi, K.; Kimata, S.; Yoshida, K.; Tanaka, M.; Aida, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2823-2825.
44. (a) For an excellent review concerning enantiosetective molecular recognition, see: Webb, T. H.; Wilcox, C. S. Chem. Soc. Rev. 1993, 383-395. (b) Partial chiral resolution of dicarboxylic acids, but not dicarboxylate anions, was achieved using chiral spirobifluorene and helicopodand skeletons functionalized with amidopyridine binding sites: Alcazar, V.; Diederich, F. Angew. Chem. Int. Ed. Engl 1992, 31, 1521-1523. See also ref 5f. A chiral binaphthyl spacer placed between two (acylamino)pyridine binding moieties has also allowed a level of enantioselective differentiation in the case of tartaric acid. See ref 10a and Garcia-Tellado, F.; Albert, J.; Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1991, 1761-1763. Enantioselective complexation of N-Cbz-L-glutamic acid was observed using cage-like receptors: Pieters, R. J.; Diederich. F. Chem. Commun. 1996, 2255-2256. (e) The inherent right-handed helicity of poly(L-glutamic acid) was recently recognized using a chiral metalloporphyrin receptor: Konishi, K.; Kimata, S.; Yoshida, K.; Tanaka, M.; Aida, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2823-2825.
45. (a) For an excellent review concerning enantiosetective molecular recognition, see: Webb, T. H.; Wilcox, C. S. Chem. Soc. Rev. 1993, 383-395. (b) Partial chiral resolution of dicarboxylic acids, but not dicarboxylate anions, was achieved using chiral spirobifluorene and helicopodand skeletons functionalized with amidopyridine binding sites: Alcazar, V.; Diederich, F. Angew. Chem. Int. Ed. Engl 1992, 31, 1521-1523. See also ref 5f. A chiral binaphthyl spacer placed between two (acylamino)pyridine binding moieties has also allowed a level of enantioselective differentiation in the case of tartaric acid. See ref 10a and Garcia-Tellado, F.; Albert, J.; Hamilton, A. D. J. Chem. Soc., Chem. Commun. 1991, 1761-1763. Enantioselective complexation of N-Cbz-L-glutamic acid was observed using cage-like receptors: Pieters, R. J.; Diederich. F. Chem. Commun. 1996, 2255-2256. (e) The inherent right-handed helicity of poly(L-glutamic acid) was recently recognized using a chiral metalloporphyrin receptor: Konishi, K.; Kimata, S.; Yoshida, K.; Tanaka, M.; Aida, T. Angew. Chem., Int. Ed. Engl. 1996, 35, 2823-2825.
46. A portion of this work, namely that describing the synthesis and carboxylate recognition/transport properties of sapphyrin dimer 2, has been previously reported in the form of a communication: Král, V.; Andrievsky, A.; Sessler, J. L. J. Am. Chem. Soc. 1995, 117, 2953-2954.
47. For reviews of sapphyrin and other "expanded" porphyrins, see: (a) Sessler, J. L.; Burrell, A. K. Top. Curr. Chem. 1991, 161, 176-273. (b) Sessler, J. L.; Burrell, A. K.; Furuta, H.; Hemmi, G. W.; Iverson, B. L.; Král, V.; Magda, D. J.; Mody, T. D.; Shreder, K.; Smith, D.; Weghorn, S. J. in Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi, A., Eds., NATO ASI Series; Kluwer: Amsterdam, 1994; pp 391-408. Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: London, 1997. Sessler, J. L.; Cyr, M., Furuta, H.; Král, V.; Mody, T.; Morishima, T.; Shionoya, M.; Weghorn, S. Pure Appl. Chem. 1993, 65, 393-398. (e) Iverson, B. L.; Shreder, K.; Král, V.; Smith, D. A.; Smith, J.; Sessler, J. L. Pure Appl. Chem. 1994, 66, 845-850.
48. For reviews of sapphyrin and other "expanded" porphyrins, see: (a) Sessler, J. L.; Burrell, A. K. Top. Curr. Chem. 1991, 161, 176-273. (b) Sessler, J. L.; Burrell, A. K.; Furuta, H.; Hemmi, G. W.; Iverson, B. L.; Král, V.; Magda, D. J.; Mody, T. D.; Shreder, K.; Smith, D.; Weghorn, S. J. in Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi, A., Eds., NATO ASI Series; Kluwer: Amsterdam, 1994; pp 391-408. Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: London, 1997. Sessler, J. L.; Cyr, M., Furuta, H.; Král, V.; Mody, T.; Morishima, T.; Shionoya, M.; Weghorn, S. Pure Appl. Chem. 1993, 65, 393-398. (e) Iverson, B. L.; Shreder, K.; Král, V.; Smith, D. A.; Smith, J.; Sessler, J. L. Pure Appl. Chem. 1994, 66, 845-850.
49. For reviews of sapphyrin and other "expanded" porphyrins, see: (a) Sessler, J. L.; Burrell, A. K. Top. Curr. Chem. 1991, 161, 176-273. (b) Sessler, J. L.; Burrell, A. K.; Furuta, H.; Hemmi, G. W.; Iverson, B. L.; Král, V.; Magda, D. J.; Mody, T. D.; Shreder, K.; Smith, D.; Weghorn, S. J. in Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi, A., Eds., NATO ASI Series; Kluwer: Amsterdam, 1994; pp 391-408. Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: London, 1997. Sessler, J. L.; Cyr, M., Furuta, H.; Král, V.; Mody, T.; Morishima, T.; Shionoya, M.; Weghorn, S. Pure Appl. Chem. 1993, 65, 393-398. (e) Iverson, B. L.; Shreder, K.; Král, V.; Smith, D. A.; Smith, J.; Sessler, J. L. Pure Appl. Chem. 1994, 66, 845-850.
50. For reviews of sapphyrin and other "expanded" porphyrins, see: (a) Sessler, J. L.; Burrell, A. K. Top. Curr. Chem. 1991, 161, 176-273. (b) Sessler, J. L.; Burrell, A. K.; Furuta, H.; Hemmi, G. W.; Iverson, B. L.; Král, V.; Magda, D. J.; Mody, T. D.; Shreder, K.; Smith, D.; Weghorn, S. J. in Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi, A., Eds., NATO ASI Series; Kluwer: Amsterdam, 1994; pp 391-408. Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: London, 1997. Sessler, J. L.; Cyr, M., Furuta, H.; Král, V.; Mody, T.; Morishima, T.; Shionoya, M.; Weghorn, S. Pure Appl. Chem. 1993, 65, 393-398. (e) Iverson, B. L.; Shreder, K.; Král, V.; Smith, D. A.; Smith, J.; Sessler, J. L. Pure Appl. Chem. 1994, 66, 845-850.
51. For reviews of sapphyrin and other "expanded" porphyrins, see: (a) Sessler, J. L.; Burrell, A. K. Top. Curr. Chem. 1991, 161, 176-273. (b) Sessler, J. L.; Burrell, A. K.; Furuta, H.; Hemmi, G. W.; Iverson, B. L.; Král, V.; Magda, D. J.; Mody, T. D.; Shreder, K.; Smith, D.; Weghorn, S. J. in Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi, A., Eds., NATO ASI Series; Kluwer: Amsterdam, 1994; pp 391-408. Sessler, J. L.; Weghorn, S. J. Expanded, Contracted, and Isomeric Porphyrins; Elsevier: London, 1997. Sessler, J. L.; Cyr, M., Furuta, H.; Král, V.; Mody, T.; Morishima, T.; Shionoya, M.; Weghorn, S. Pure Appl. Chem. 1993, 65, 393-398. (e) Iverson, B. L.; Shreder, K.; Král, V.; Smith, D. A.; Smith, J.; Sessler, J. L. Pure Appl. Chem. 1994, 66, 845-850.
52. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
53. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
54. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
55. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
56. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
57. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
58. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
59. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
60. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
61. (a) Král, V.; Furuta, H.; Shreder, K.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1595-1607. (b) Iverson, B. L.; Shreder, K.; Král, V.; Sansom, P. I.; Lynch, V.; Sessler, J. L. J. Am. Chem. Soc. 1996, 118, 1608-1616. Sessler, J. L.; Cyr, M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810-2813. Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714-5722. (e) Král, V.; Sessler, J. L.; Furuta, H. J. Am. Chem. Soc. 1992, 114, 8704-8705. (f) Sessler, J. L.; Furuta, H.; Král, V. Supramol Chem. 1993, 1, 209-220. (g) Král, V.; Sessler, J. L. Tetrahedron, 1995, 51, 539-554. (h) Sessler, J. L.; Andrievsky, A. Chem. Commun. 1996, 1119-1120. Král, V.; Andrievsky, A.; Sessler, J. L. J. Chem. Soc., Chem. Commun. 1995, 2349-2351. (j) Sessler, J. L.; Sansom, P. I.; Král, V.; O'Connor, D.; Iverson, B. L. J. Am. Chem. Soc. 1996, 118, 12323-12330.
62. Generally, the bound anionic substrates are held above the plane of the sapphyrin macrocycle. This generalization appears to be true for all anions except fluoride. This latter species fits perfectly inside the sapphyrin cavity and is bound exceedingly well by sapphyrin mono- and dication (c.f.; ref 14d).
63. Tarbell, D. S.; Yamamoto, Y.; Pope, B. M. Proc. Natl Acad. Sci. U.S.A. 1972, 69, 730-732.
64. Lockley, W. J. S. J. Labelled Compd. Radiopharm. 1984, 21, 45-57.
65. Tsukube, H. in Liquid Membranes: Chemical Applications; Araki, T., Tsukube, H., Eds., CRC Press: Boca Raton, FL, 1990.
66. Connors, K. A. Binding Constants. The Measurement of Molecular Complex Stability; Wiley: New York, 1987.
67. See, for instance: Bailey, P. D. An Introduction to Peptide Chemistry; Wiley: Chichester. 1990.
68. Whiteford, J. A.; Rachlin, E. M.; Stang, P. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 2524-2529 and references therein.
69. -4 M.
70. (a) Valdes-Aguilera, O.; Neckers, D. C. Acc. Chem. Res. 1989, 22, 171-177.
71. (b) Ojadi, E.; Selzer, R.; Linschitz, H. J. Am. Chem. Soc. 1985, 107, 7784-7785.
72. These changes result strictly from anion chelation by the dimer 2 and not from the protonation of its constituent sapphyrin macrocycles. This is because the substrates are studied in the form of their dicarboxylate salts, rather than as the free acids. They therefore lack "free" protons that could be transferred to the sapphyrin.
73. The linear character of these plots is consistent with the proposed 1:1 stoichiometry. This contention is further supported by the fact that both the low and high energy Soret bands of dimer 2 obey Beer's law over the course of the concentration regime used for the binding studies. The equilibria followed this way are thus strictly bimolecular in nature.
74. This extra stabilization presumably also leads to the higher binding affinities observed for the aromatic monocarboxylate controls (Table 2).
75. π-π interactions featuring face-to-face orientations between aromatic surfaces as well as edge-to-face C - H⋯π attractions have been shown to stabilize various supramolecular complexes. See: (a) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-5534. (b) Hunter, C. A. Chem. Soc. Rev. 1994, 101-109. The C - H⋯N binding motif, although not as common, has also been observed in certain noncovalent supramolecular aggregates. See: (c) Berkovitch-Yellin, Z., Leiserowitz, L. Acta Crystallogr. 1984, B40, 159-165. Allen, F. H.; Goud, B. S.; Hoy, V. J.; Howard, J. A. K.; Desiraju, G. R. J Chem. Soc., Chem. Commun. 1994, 2729-2730.
76. π-π interactions featuring face-to-face orientations between aromatic surfaces as well as edge-to-face C - H⋯π attractions have been shown to stabilize various supramolecular complexes. See: (a) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-5534. (b) Hunter, C. A. Chem. Soc. Rev. 1994, 101-109. The C - H⋯N binding motif, although not as common, has also been observed in certain noncovalent supramolecular aggregates. See: (c) Berkovitch-Yellin, Z., Leiserowitz, L. Acta Crystallogr. 1984, B40, 159-165. Allen, F. H.; Goud, B. S.; Hoy, V. J.; Howard, J. A. K.; Desiraju, G. R. J Chem. Soc., Chem. Commun. 1994, 2729-2730.
77. π-π interactions featuring face-to-face orientations between aromatic surfaces as well as edge-to-face C - H⋯π attractions have been shown to stabilize various supramolecular complexes. See: (a) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-5534. (b) Hunter, C. A. Chem. Soc. Rev. 1994, 101-109. The C - H⋯N binding motif, although not as common, has also been observed in certain noncovalent supramolecular aggregates. See: (c) Berkovitch-Yellin, Z., Leiserowitz, L. Acta Crystallogr. 1984, B40, 159-165. Allen, F. H.; Goud, B. S.; Hoy, V. J.; Howard, J. A. K.; Desiraju, G. R. J Chem. Soc., Chem. Commun. 1994, 2729-2730.
78. π-π interactions featuring face-to-face orientations between aromatic surfaces as well as edge-to-face C - H⋯π attractions have been shown to stabilize various supramolecular complexes. See: (a) Hunter, C. A.; Sanders, J. K. M. J. Am. Chem. Soc. 1990, 112, 5525-5534. (b) Hunter, C. A. Chem. Soc. Rev. 1994, 101-109. The C - H⋯N binding motif, although not as common, has also been observed in certain noncovalent supramolecular aggregates. See: (c) Berkovitch-Yellin, Z., Leiserowitz, L. Acta Crystallogr. 1984, B40, 159-165. Allen, F. H.; Goud, B. S.; Hoy, V. J.; Howard, J. A. K.; Desiraju, G. R. J Chem. Soc., Chem. Commun. 1994, 2729-2730.
79. The use of peptidic moieties for the construction of enantioselective receptors is borrowed from nature. A desire to understand the molecular recognition features of proteins has inspired development of abiotic receptors containing amide moieties. Groups that champion this approach have been able to achieve remarkable enantioselectivities in the binding of amino acids and short peptidic substrates, (a) For a short review, see: Schneider, H.-J. Angew. Chem., Int. Ed. Engl. 1993, 32, 848-850. See also: (b) Yoon, S. S.; Still, W. C. J. Am. Chem. Soc. 1993, 115, 823-824. Hong, J.-I.; Namgoong, S. K.; Bernardi, A.; Still, W. C. J. Am. Chem. Soc. 1991, 113, 5111-5112. See also ref 11d.
80. The use of peptidic moieties for the construction of enantioselective receptors is borrowed from nature. A desire to understand the molecular recognition features of proteins has inspired development of abiotic receptors containing amide moieties. Groups that champion this approach have been able to achieve remarkable enantioselectivities in the binding of amino acids and short peptidic substrates, (a) For a short review, see: Schneider, H.-J. Angew. Chem., Int. Ed. Engl. 1993, 32, 848-850. See also: (b) Yoon, S. S.; Still, W. C. J. Am. Chem. Soc. 1993, 115, 823-824. Hong, J.-I.; Namgoong, S. K.; Bernardi, A.; Still, W. C. J. Am. Chem. Soc. 1991, 113, 5111-5112. See also ref 11d.
81. The use of peptidic moieties for the construction of enantioselective receptors is borrowed from nature. A desire to understand the molecular recognition features of proteins has inspired development of abiotic receptors containing amide moieties. Groups that champion this approach have been able to achieve remarkable enantioselectivities in the binding of amino acids and short peptidic substrates, (a) For a short review, see: Schneider, H.-J. Angew. Chem., Int. Ed. Engl. 1993, 32, 848-850. See also: (b) Yoon, S. S.; Still, W. C. J. Am. Chem. Soc. 1993, 115, 823-824. Hong, J.-I.; Namgoong, S. K.; Bernardi, A.; Still, W. C. J. Am. Chem. Soc. 1991, 113, 5111-5112. See also ref 11d.
82. Binaphthalene and diaminocyclohexane spacers were previously used in chiral receptors for dicarboxylic acids (ref 11c) and short peptides (ref 28b).
83. No traces of larger macrocycles were found in the reaction mixture.
84. For recent reports on the syntheses and applications of covalently-linked chiral porphyrin dimers, see: (a) Ema, T.; Nemugaki, S.; Tsuboi, S.; Utaka, M. Tetrahedron Lett. 1995, 36, 5905-5908 and references therein. (b) Crossley, M. J.; Mackay, L. G.; Try, A. J. Chem. Soc., Chem. Commun. 1995, 1925-1927.
85. For recent reports on the syntheses and applications of covalently-linked chiral porphyrin dimers, see: (a) Ema, T.; Nemugaki, S.; Tsuboi, S.; Utaka, M. Tetrahedron Lett. 1995, 36, 5905-5908 and references therein. (b) Crossley, M. J.; Mackay, L. G.; Try, A. J. Chem. Soc., Chem. Commun. 1995, 1925-1927.
86. For reviews about dimeric porphyrins, see: (a) Collman, J. P.; Wagenknecht, P. S.; Hutchison, J. E. Angew. Chem., Int. Ed. Engl. 1994, 33, 1537-1554. (b) Wasielewski, M. Chem. Rev. 1992, 92, 435-461.
87. For reviews about dimeric porphyrins, see: (a) Collman, J. P.; Wagenknecht, P. S.; Hutchison, J. E. Angew. Chem., Int. Ed. Engl. 1994, 33, 1537-1554. (b) Wasielewski, M. Chem. Rev. 1992, 92, 435-461.
88. For reviews, see: (a) Kilberg, M. S., Häussinger, D., Eds. Mammalian Amino Acid Transport. Mechanisms and Control; Plenum Press: New York, 1992. (b) Kilberg, M. S.; Stevens, B. R.; Novak. D. A. Annu. Rev. Nutr. 1993, 13, 137-165. Ring, K. Angew. Chem., Int. Ed. Engl. 1970, 9, 345-356. See also ref 4.
89. For reviews, see: (a) Kilberg, M. S., Häussinger, D., Eds. Mammalian Amino Acid Transport. Mechanisms and Control; Plenum Press: New York, 1992. (b) Kilberg, M. S.; Stevens, B. R.; Novak. D. A. Annu. Rev. Nutr. 1993, 13, 137-165. Ring, K. Angew. Chem., Int. Ed. Engl. 1970, 9, 345-356. See also ref 4.
90. For reviews, see: (a) Kilberg, M. S., Häussinger, D., Eds. Mammalian Amino Acid Transport. Mechanisms and Control; Plenum Press: New York, 1992. (b) Kilberg, M. S.; Stevens, B. R.; Novak. D. A. Annu. Rev. Nutr. 1993, 13, 137-165. Ring, K. Angew. Chem., Int. Ed. Engl. 1970, 9, 345-356. See also ref 4.
91. Reports of binding and/or transport of aspartic and glutamic acids and their derivatives in either neutral or anionic forms are relatively scarce: (a) Inokuma, S.; Sakai, S.; Yamamoto, T.; Nishimura, J. J. Membr. Sci. 1994, 97, 175-183.
92. (b) Flack, S. S.; Chaumette, J.-L.; Kilburn, J. D.; Langley, G. J.; Webster, M. J. Chem. Soc., Chem. Commun. 1993, 399-401. See also refs 5e, 6a, and 7c. Enantioselective binding of neutral aspartic and glutamic acids and their derivatives was reported by Diederich: ref 11b,d.
93. It proved necessary to use this solvent mixture so as to enforce the concurrent solubility of the receptors, substrates, and complexes under consideration.
94. In all cases (using chiral receptors 3, 4, and 7), the weaker bound dicarboxylates were also the ones that were found to allow for a higher level of enantiosefective discrimination between their respective enantiomer pairs.