Synthesis and aggregation of a conjugated helical molecule

Journal of the American Chemical Society

Volumn 121, Issue 1, 1999, Pages 79-88

  Nuckolls, Colin ^a   Katz, Thomas J ^a   Katz, Gail ^a   Collings, Peter J ^b   Castellanos, Louis ^a  

^a Columbia University ^*  (United States)

^b SWARTHMORE COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HELICENEBISQUINONE; QUINONE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CIRCULAR DICHROISM; ENANTIOMER; LIGHT SCATTERING; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; ULTRAVIOLET SPECTROPHOTOMETRY;

EID: 0033550487     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983248l     Document Type: Article

References (94)

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5. This was first shown by Peter Collings (see ref 1).
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7. A derivative of 1 was recently found to be the first core-chiral columnar liquid crystal: Nuckolls, C.; Katz, T. J. J. Am. Chem. Soc. 1998, 120, 9541.
8. 11CO groups in place of the acetyls, the last compound in water (Colin Nuckolls, Thomas J. Katz, and Louis Castellanos, unpublished results).
9. The reactions of bis(enol ether)s of arylmethyl ketones with p-benzoquinone have given a number of helicenebisquinones: (a) Willmore, N. D.; Liu, L.; Katz, T. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1093. (b) Katz, T. J.; Liu, L.; Willmore, N. D.; Fox, J. M.; Rheingold, A. L.; Shi, S.; Nuckolls, C.; Rickman, B. H. J. Am. Chem. Soc. 1997, 119, 10054. (c) Fox, J. M.; Goldberg, N. R.; Katz, T. J. J. Org. Chem. 1998, 63, 7456.
10. The reactions of bis(enol ether)s of arylmethyl ketones with p- benzoquinone have given a number of helicenebisquinones: (a) Willmore, N. D.; Liu, L.; Katz, T. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1093. (b) Katz, T. J.; Liu, L.; Willmore, N. D.; Fox, J. M.; Rheingold, A. L.; Shi, S.; Nuckolls, C.; Rickman, B. H. J. Am. Chem. Soc. 1997, 119, 10054. (c) Fox, J. M.; Goldberg, N. R.; Katz, T. J. J. Org. Chem. 1998, 63, 7456.
11. The reactions of bis(enol ether)s of arylmethyl ketones with p- benzoquinone have given a number of helicenebisquinones: (a) Willmore, N. D.; Liu, L.; Katz, T. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1093. (b) Katz, T. J.; Liu, L.; Willmore, N. D.; Fox, J. M.; Rheingold, A. L.; Shi, S.; Nuckolls, C.; Rickman, B. H. J. Am. Chem. Soc. 1997, 119, 10054. (c) Fox, J. M.; Goldberg, N. R.; Katz, T. J. J. Org. Chem. 1998, 63, 7456.
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15. 1H NMR spectrum of two meta-coupled aromatic hydrogens, one at very low fields, and the acetyl group. The spectrum (400 MHz) displays the former at δ 8.39 and 7.66 ppm (both 1 H, d, J = 1.6 Hz) and the latter at 2.67 ppm (3 H, s). In addition, there are the following resonances: two sharp singlets, at 7.76 and 7.57 ppm (both 1 H), expected from the other aromatic hydrogens; an AB quartet at 7.07 and 6.98 ppm (J = 10 Hz), attributable to the quinone hydrogens; a broad singlet at 1.48 ppm (18 H), attributable to the pivalates; and the two singlets expected from the TBDMS group, at 1.08 and 0.39 ppm (9 and 6 H, respectively).
16. The adsorbants tried were silica gel, silica gel doped with triethylamine, basic alumina, neutral alumina, and florisil. The lability is presumed to be associated with conjugation between the siloxyls and the quinone's carbonyls. Other helical derivatives of 6-siloxy-1,4-naphthoquinone prepared in our lab proved less sensitive. They decomposed only slightly when chromatographed (ref 9b,c and S. Dreher, unpublished results).
17. 1H NMR spectrum of the desired product is easily identified because it consists of two very sharp singlets and an AB quartet.
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32. Reference 9c and unpublished results by a number of co-workers in our lab.
33. Commercially available and easily prepared (Gerlach, H.; Kappes, D.; Boeckman, R. K., Jr.; Maw, G. N. Organic Syntheses; Wiley: New York, 1998; Collect. Vol. IX, p 151).
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39. Also formed in this reaction was a triacetate, presumably a material with the two acetoxy groups of 3 and one other.
40. 1H FT-NMR Spectra, Edition 1, Vol. 2; Aldrich Chemical Co.: Milwaukee, 1993; pp 1298C and 1285B.
41. Dai, Y.; Katz, T. J. J. Org. Chem. 1997, 62, 1274. In addition, this reference shows a similar effect applies to isobutyrate esters.
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44. By the method described in ref 9b.
45. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
46. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
47. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
48. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
49. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
50. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
51. For examples in which the CDs of aggregating molecules are enhanced by concentration see footnote 4 in ref 1 and (a) Gottarelli, G.; Mezzina, E.; Spada, G. P.; Carsughi, F.; Di Nicola, G.; Mariani, P.; Sabatucci, A.; Bonazzi, S. Helv. Chim. Acta 1996, 79, 220 and references therein. For examples in which solvents and temperature are the agents of change, see: (b) Palmans, A. R. A.; Vekemans, J. A. J. M.; Havinga, E. E.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1997, 36, 2648. (c) Matile, S.; Berova, N.; Nakanishi, K. Chem. Biol. 1996, 3, 379. (d) Huang, D.; Matile, S.; Berova, N.; Nakanishi, K. Heterocycles 1996, 42, 723 and references therein. (e) Schnur, J. M.; Ratna, B. R.; Selinger, J V.; Singh, A.; Jyothi, G.; Easwaran, K. R. K. Science 1994, 264, 945. For examples in which organization in films results in enhanced CD spectra, see ref 37b. Also see: (f) van Nostrum, C. F.; Bosman, A. W.; Gelinck, G. H.; Schouten, P. G.; Warman, J. M.; Kentgens, A. P. M.; Devillers, M. A. C.; Meijerink, A.; Picken, S. J.; Sohling, U.; Schouten, A.-J.; Nolte, R. J. M. Chem. Eur. J. 1995, 1, 171. (g) Barberá, J.; Iglesias, R.; Serrano, J. L.; Sierra, T.; de la Fuente, M. R.; Palacios, B.; Pérez-Jubindo, M. A.; Vázquez, J. T. J. Am. Chem. Soc. 1998, 120, 2908.
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65. Molecules whose solutions are either viscous or gel include, besides many that hydrogen-bond to one another, a number that are united by π-stacking forces: (a) Scheibe, G. Kolloid-Z. 1938, 82, 1. (b) Lin, Y.; Kachar, B.; Weiss, R. G. J. Am. Chem. Soc. 1989, 111, 5542. (c) Snijder, C. S.; de Jong, J. C.; van Bolhuis, F.; Feringa, B. L. Chem. Eur. J. 1995, 1, 594. (d) van Nostrum, C. F.; Picken, S. J.; Schouten, A.-J.; Nolte, R. J. M. J. Am. Chem. Soc. 1995, 117, 9957. (e) Brotin, T.; Utermöhlen, R.; Fages, F.; Bouas-Laurent, H.; Desvergne, J.-P. J. Chem. Soc., Chem. Commun. 1991, 416.
66. Molecules whose solutions are either viscous or gel include, besides many that hydrogen-bond to one another, a number that are united by π-stacking forces: (a) Scheibe, G. Kolloid-Z. 1938, 82, 1. (b) Lin, Y.; Kachar, B.; Weiss, R. G. J. Am. Chem. Soc. 1989, 111, 5542. (c) Snijder, C. S.; de Jong, J. C.; van Bolhuis, F.; Feringa, B. L. Chem. Eur. J. 1995, 1, 594. (d) van Nostrum, C. F.; Picken, S. J.; Schouten, A.-J.; Nolte, R. J. M. J. Am. Chem. Soc. 1995, 117, 9957. (e) Brotin, T.; Utermöhlen, R.; Fages, F.; Bouas-Laurent, H.; Desvergne, J.-P. J. Chem. Soc., Chem. Commun. 1991, 416.
67. Molecules whose solutions are either viscous or gel include, besides many that hydrogen-bond to one another, a number that are united by π-stacking forces: (a) Scheibe, G. Kolloid-Z. 1938, 82, 1. (b) Lin, Y.; Kachar, B.; Weiss, R. G. J. Am. Chem. Soc. 1989, 111, 5542. (c) Snijder, C. S.; de Jong, J. C.; van Bolhuis, F.; Feringa, B. L. Chem. Eur. J. 1995, 1, 594. (d) van Nostrum, C. F.; Picken, S. J.; Schouten, A.-J.; Nolte, R. J. M. J. Am. Chem. Soc. 1995, 117, 9957. (e) Brotin, T.; Utermöhlen, R.; Fages, F.; Bouas-Laurent, H.; Desvergne, J.-P. J. Chem. Soc., Chem. Commun. 1991, 416.
68. Molecules whose solutions are either viscous or gel include, besides many that hydrogen-bond to one another, a number that are united by π-stacking forces: (a) Scheibe, G. Kolloid-Z. 1938, 82, 1. (b) Lin, Y.; Kachar, B.; Weiss, R. G. J. Am. Chem. Soc. 1989, 111, 5542. (c) Snijder, C. S.; de Jong, J. C.; van Bolhuis, F.; Feringa, B. L. Chem. Eur. J. 1995, 1, 594. (d) van Nostrum, C. F.; Picken, S. J.; Schouten, A.-J.; Nolte, R. J. M. J. Am. Chem. Soc. 1995, 117, 9957. (e) Brotin, T.; Utermöhlen, R.; Fages, F.; Bouas-Laurent, H.; Desvergne, J.-P. J. Chem. Soc., Chem. Commun. 1991, 416.
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74. (e) Cornell, D. G. J. Colloid Interface Sci., 1979, 70, 167.
75. -2 (Langeveld-Voss, B. M. W.; Janssen, R. A. J.; Christiaans, M. P. T.; Meskers, S. C. J.; Dekkers, H. P. J. M.; Meijer, E. W. J. Am. Chem. Soc. 1996, 118, 4908).
76. Similar effects of solvents on the films of phthalocyanines have been attributed to the formation of a lyotropic phase (Fujiki, M.; Tabei, H.; Kurihara, T. Langmuir 1988, 4, 1123).
77. 2)/g.
78. This sample was made by sandwiching 1 between quartz plates that were separated by a 2 μm aluminum spacer from The Goodfellow Corp., Berwyn, PA.
79. 1 to be 0.85 g/mL.
80. Katz, T. J.; Sudhakar, A.; Teasley, M. F.; Gilbert, A. M.; Geiger, W. E.; Robben, M. P.; Wuensch, M.; Ward, M. D. J. Am. Chem. Soc. 1993, 115, 3182.
81. Muševič, I.; Škarabot, M.; Kityk, A. V.; Blinc, R.; Moro, D.; Heppke, G. Ferroelectrics 1997, 205, 133.
82. (a) de Vries, H. Acta Crystallogr. 1951, 4, 219.
83. (b) Chandrasekhar, S.; Prasad, J. S. Mol. Cryst. Liq. Cryst. 1971, 14, 115.
84. (c) Isaert, N.; Berthault, J.-P.; Billard, J. J. Opt. 1980, 11, 17.
85. (d) Cano, R.; Chatelain, P. Compt. Rend. 1964, 259, 352.
86. (e) Baessler, H.; Laronge, T. M.; Labes, M. M. J. Chem. Phys. 1969, 51, 3213.
87. The notion that π-donor-acceptor interactions stabilize aggregating columnar systems was also proposed by others: ref 38a,b. Also see: (a) Green, M. M.; Ringsdorf, H.; Wagner, J.; Wüstefeld, R. Angew. Chem., Int. Ed. Engl. 1990, 29, 1478 and references therein. (b) Mohr, B.; Wegner, G.; Ohta, K. J. Chem. Soc., Chem. Commun. 1995, 995.
88. The notion that π-donor-acceptor interactions stabilize aggregating columnar systems was also proposed by others: ref 38a,b. Also see: (a) Green, M. M.; Ringsdorf, H.; Wagner, J.; Wüstefeld, R. Angew. Chem., Int. Ed. Engl. 1990, 29, 1478 and references therein. (b) Mohr, B.; Wegner, G.; Ohta, K. J. Chem. Soc., Chem. Commun. 1995, 995.
89. 1 the DSC was scanned to only 210 °C and therefore just missed the phase transitions recorded here.
90. (a) Martin, R. H.; Marchant, M.-J. Tetrahedron Lett. 1972, 3707.
91. -1) were recalculated using the kinetic data in the first of these references.
92. Goedicke, C.; Stegemeyer, H. Tetrahedron Lett. 1970, 937.
93. See footnote 15 in ref 7.
94. See the Supporting Infomation to ref 1.