Skip to main content
SpringerLink
Log in

Macrocyclic Structurally Homoconjugated Oligoacetylenes: Acetylene- and Diacetylene-Expanded Cycloalkanes and Rotanes

  • Chapter
  • First Online:
Carbon Rich Compounds II, Macrocyclic Oligoacetylenes and Other Linearly Conjugated Systems

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 201))

Abstract

There is ample evidence for the significance of modern acetylene chemistry and its role for the future development in several areas of organic chemistry. In this chapter, the successful syntheses and attempted approaches to macrocyclic structurally homoconjugated oligoacetylenes and oligodiacetylenes, as well as some of their physical properties, are discussed. Such compounds, which are formally derived from permethylated cycloalkanes by insertion of -C≡C- or -C≡C-C≡C-fragments between each pair of adjacent sp 3-hybridized carbon atoms, have been termed [n]pericyclines and expanded [n]pericyclines, respectively. These and analogous hydrocarbons formally derived from [n]rotanes (perspirocyclopropanated [n]pericyclines and “exploded” [n]rotanes) as well as heteroanalogues of [n]pericyclines are presented. In addition, the preparations and properties of macrocycles with mixed ethyne and butadiyne expanders as well as the attempted syntheses of perspirocyclopropanated “exploded” [n]rotanes are also covered. In view of the reported properties, the question of cyclic homoconjugation and homoaromaticity in these unconventional compounds is discussed. Finally, some chemical transformations of these macrocyclic oligoacetylenes and oligodiacetylenes, e.g. the conversion of diacetylene-expanded [n]rotanes into crowns of thiophenes, are presented.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
eBook
USD 16.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 16.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. McQuilkin RM, Garratt PJ, Sondheimer F (1970) J Am Chem Soc 92:6682

    Article  Google Scholar 

  2. Sond-heimer F (1963) Pure Appl Chem 7:363

    Article  CAS  Google Scholar 

  3. Diederich F, Stang PJ (1998) Metal-catalyzed cross-coupling reactions. Wiley-VCH, Weinheim

    Google Scholar 

  4. Stang PJ, Diederich F (1995) Modern acetylene chemistry. VCH, Weinheim

    Google Scholar 

  5. Scott LT, Cooney MJ (1995) Macrocyclic homoconjugated polyacetylenes. In: Stang PJ, Diederich F (eds) Modern acetylene chemistry. VCH, Weinheim, p 321

    Chapter  Google Scholar 

  6. Scott LT, DeCicco GJ, Hyun JL, Reinhardt G (1983) J Am Chem Soc 105:7760

    Article  CAS  Google Scholar 

  7. Scott LT, DeCicco GJ, Hyun JL, Reinhardt G (1985) J Am Chem Soc 107:6546

    Article  CAS  Google Scholar 

  8. Scott LT, Cooney MJ, Johnels D (1990) J Am Chem Soc 112:4054

    Article  CAS  Google Scholar 

  9. Roth WR, Staemmler V, Neumann M, Schmuck C (1995) Liebigs Ann 1061

    Google Scholar 

  10. de Meijere A (1979) Angew Chem Int Ed Engl 18:809

    Article  Google Scholar 

  11. Wiberg KB (1997) In: de Meijere A (ed) Houben-Weyl, Thieme, Stuttgart, vol E17a, p 1

    Google Scholar 

  12. Eckert-Maksic M, Gleiter R, Zefirov NS, Kozhushkov SI, Kuznetsova TS (1991) Chem Ber 124:371

    Article  CAS  Google Scholar 

  13. Gleiter R, Spanget-Larsen J (1992) In: Halton B (ed) Advances in strain in organic chemistry. vol 2, JAI Press, London, p 143

    Google Scholar 

  14. de Meijere A, Kozhushkov SI, Scott LT, Cooney MJ, Gleiter R unpublished results

    Google Scholar 

  15. de Meijere A, Jaekel F, Simon A, Borrmann H, Köhler J, Johnels D, Scott LT (1991) J Am Chem Soc 113:3935

    Article  Google Scholar 

  16. Jaekel F (1988) Dissertation, Universität Hamburg

    Google Scholar 

  17. Otte C (1994) Dissertation, Universität Göttingen

    Google Scholar 

  18. Köbrich G, Merkel D (1970) Angew Chem Int Ed Engl 9:243

    Article  Google Scholar 

  19. Köbrich G, Merkel D, Thiem K-W (1972) Chem Ber 105:1683

    Article  Google Scholar 

  20. Militzer H-C, Schömenauer S, Otte C, Puls C, Hain J, Bräse S, de Meijere A (1993) Synthesis 998

    Google Scholar 

  21. Scott LT, Cooney MJ, Otte C, Puls C, Haumann T, Boese R, Carroll PJ, Smith AB, III, de Meijere A (1994) J Am Chem Soc 116:10275

    Article  CAS  Google Scholar 

  22. Scott LT, Unno M (1990) J Am Chem Soc 112:7823

    Article  CAS  Google Scholar 

  23. Voronkov MG, Yarosh OG, Zhilitskaya LV, Albanov AI, Vitkovskii VYu (1991) Metalloorg Khim 4:368, (1991) Chem Abstr 115:29446d

    CAS  Google Scholar 

  24. Voronkov MG, Pavlov SF (1973) J Gen Chem USSR (Engl Transl) 43:1397, (1973) Chem Abstr 79:66448q

    Google Scholar 

  25. Hengge E, Baumegger A (1989) J Organomet Chem 369:C39

    Article  CAS  Google Scholar 

  26. Bortolin R, Parbhoo B, Brown SSD (1988) J Chem Soc Chem Commun 1079

    Google Scholar 

  27. Sakurai H, Eriyama Y, Hosomi A, Nakadaira Y, Kabuto C (1984) Chem Lett 595

    Google Scholar 

  28. Houk KN, Scott LT, Rondan NG, Spellmeyer DC, Reinhardt G, Hyun JL, DeCicco GJ, Weiss R, Chen MHM, Bass LS, Clardy J, Jørgensen FS, Eaton TA, Sarkozi V, Petit CM, Ng L, Jordan KD (1985) J Am Chem Soc 107:6556

    Article  CAS  Google Scholar 

  29. Baumegger A, Hengge E, Gamper S, Hardtweck E, Janoschek R (1991) Monatsh Chem 122:661

    Article  CAS  Google Scholar 

  30. Scott LT, Cooney MJ, Rogers DW, Dejroongruang K (1988) J Am Chem Soc 110:7244

    Article  CAS  Google Scholar 

  31. Dewar MJS, Holloway MK (1984) J Chem Soc Chem Commun 1188

    Google Scholar 

  32. Schaad LJ, Hess BA Jr, Scott LT (1993) J Phys Org Chem 6:316

    Article  CAS  Google Scholar 

  33. Jiao H, van Eikema Hommes NJR, Schleyer PvR, de Meijere A (1996) J Org Chem 61:2826

    Article  CAS  Google Scholar 

  34. Haumann T, Boese R, Kozhushkov SI, Rauch K, de Meijere A (1997) Liebigs Ann/Recueil 2047

    Google Scholar 

  35. Domalski ES, Hearing ED (1988) J Phys Chem Ref Data 17:1637

    Article  CAS  Google Scholar 

  36. Kuznetsova TS (1991) Habilitation Thesis, Moscow State University

    Google Scholar 

  37. Gleiter R, Schäfer W, Sakurai H (1985) J Am Chem Soc 107:3046

    Article  CAS  Google Scholar 

  38. Verevkin SP, Beckhaus H-D, Rüchardt C, Haag R, Kozhushkov SI, Zywietz T, de Meijere A, Jiao H, Schleyer PvR (1998) J Am Chem Soc 120:in press

    Google Scholar 

  39. de Meijere A, Kozhushkov SI, Puls C, Haumann T, Boese R, Cooney MJ, Scott LT (1994) Angew Chem Int Ed Engl 33:869

    Article  Google Scholar 

  40. de Meijere A, Kozhushkov SI, Haumann T, Boese R, Puls C, Cooney MJ, Scott LT (1995) Chem Eur J 1:124

    Article  Google Scholar 

  41. Isaacs L, Seiler P, Diederich F (1995) Angew Chem Int Ed Engl 34:1466

    Article  CAS  Google Scholar 

  42. Isaacs L, Diederich F, Haldimann RF (1997) Helv Chim Acta 80:317

    Article  CAS  Google Scholar 

  43. Brake M, Enkelmann V, Bunz UHF (1996) J Org Chem 61:1190

    Article  CAS  Google Scholar 

  44. Diederich F (1995) Oligoacetylenes. In: Stang PJ, Diederich F (eds) Modern acetylene chemistry. VCH, Weinheim, p 443

    Chapter  Google Scholar 

  45. Glaser C (1869) Chem Ber 2:422

    Google Scholar 

  46. Behr OM, Eglinton G, Galbraith AR, Raphael RA (1960) J Chem Soc 3614

    Google Scholar 

  47. Hay AS (1962) J Org Chem 27:3320

    Article  CAS  Google Scholar 

  48. Cadiot P, Chodkiewicz W (1969) Couplings of acetylenes. In: Viehe HG (ed) Chemistry of acetylenes. chap 9, Dekker, New York, p 630

    Google Scholar 

  49. Roth WR, Kowalczik U, Maier G, Reisenauer HP, Sustmann R, Müller W (1987) Angew Chem Int Ed Engl 26:1285

    Article  Google Scholar 

  50. Herberich GE, Bauer E, Hengesbach J, Kölle U, Huttner G, Lorenz H (1977) Chem Ber 110:760

    Article  CAS  Google Scholar 

  51. Liese T, de Meijere A (1986) Chem Ber 119:2995

    Article  CAS  Google Scholar 

  52. Kozhushkov SI, de Meijere A unpublished results

    Google Scholar 

  53. Zefirov NS, Kozhushkov SI, Kuznetsova TS, Gleiter R, Eckert-Maksic M (1986) J Org Chem USSR (Engl Transl) 22:95

    Google Scholar 

  54. de Meijere A, Kozhushkov SI, Spaeth T, Zefirov NS (1993) J Org Chem 58:502

    Article  Google Scholar 

  55. Hauptmann H (1975) Tetrahedron Lett 1931

    Google Scholar 

  56. Hauptmann H (1976) Tetrahedron 32:1293

    Article  CAS  Google Scholar 

  57. An Y-Z, Rubin Y, Schaller C, McElvany SW (1994) J Org Chem 59:2927

    Article  CAS  Google Scholar 

  58. Anderson HL, Faust R, Rubin Y, Diederich F (1994) Angew Chem Int Ed Engl 33:1366

    Article  Google Scholar 

  59. Berscheid R, Vögtle F (1992) Synthesis 58

    Google Scholar 

  60. O’Krongly D, Denmeade SR, Chiang MY, Breslow R (1985) J Am Chem Soc 107:5544

    Article  CAS  Google Scholar 

  61. Boese R, Haumann T, Belov VN, de Meijere A unpublished results.

    Google Scholar 

  62. Prangé T, Pascard C, de Meijere A, Behrens U, Barnier J-P, Conia J-M (1980) Nouv J Chim 4:321

    Google Scholar 

  63. Saebø S, Cordell FR, Boggs JE (1983) J Mol Struct Theochem 104:221

    Article  Google Scholar 

  64. Adams WJ, Geise HJ, Bartell LS (1970) J Am Chem Soc 92:5013

    Article  CAS  Google Scholar 

  65. Allinger NL, Geise HJ, Pyckhout W, Paquette LA, Gallucci JC (1989) J Am Chem Soc 111: 1106 and references cited therein

    Article  CAS  Google Scholar 

  66. Kahn R, Fourme R, André D, Renaud M (1973) Acta Cryst B 29:131

    Article  CAS  Google Scholar 

  67. Dillen J, Geise HJ (1979) J Chem Phys 70:425

    Article  CAS  Google Scholar 

  68. Dorofeeva OV, Mastryukov VS, Allinger NL, Almenningen A (1985) J Phys Chem 89:252

    Article  CAS  Google Scholar 

  69. Siam K, Dorofeeva OV, Mastryukov VS, Ewbank JD, Allinger NL, Schäfer L (1988) J Mol Struct Theochem 164:93 and references cited therein

    Article  Google Scholar 

  70. Guo L, Bradshaw JD, Tessier CA, Youngs WJ (1994) J Chem Soc Chem Commun 243 and references cited therein

    Google Scholar 

  71. Zhou Q, Carroll PJ, Swager TM (1994) J Org Chem 59:1294

    Article  CAS  Google Scholar 

  72. Anthony J, Knobler CB, Diederich F (1993) Angew Chem Int Ed Engl 32:406

    Article  Google Scholar 

  73. Hoffmann R (1970) Tetrahedron Lett: 2907

    Google Scholar 

  74. Günther H (1970) Tetrahedron Lett: 5173

    Google Scholar 

  75. Kozhushkov SI, Haumann T, Boese R, de Meijere A unpublished results

    Google Scholar 

  76. Boese R, Haumann T, Jemmis ED, Kiran B, Kozhushkov SI, de Meijere A (1996) Liebigs Ann 913

    Google Scholar 

  77. Schleyer PvR, Williams JE, Blanchard KR (1970) J Am Chem Soc 92:2377

    Article  CAS  Google Scholar 

  78. Dewar MJS, Zoebich EG, Healy EF, Stewart JJP (1985) J Am Chem Soc 107:3902

    Article  CAS  Google Scholar 

  79. Beckhaus H-D, Verevkin S, Rüchardt C, Diederich F, Thilgen C, ter Meer H-U, Mohn H, Müller W (1994) Angew Chem Int Ed Engl 33:996

    Article  Google Scholar 

  80. Löbbecke S, Pfeil A, de Meijere A (1997) Pyrolisis of high energetic diacetylenes 28th Int Ann Conf ICT, p 111

    Google Scholar 

  81. Löbbecke S, Pfeil A (1998) Thermochimica Acta in press

    Google Scholar 

  82. Boese R, Matzger AJ, Vollhardt KPC (1997) J Am Chem Soc 119:2052

    Article  CAS  Google Scholar 

  83. For rewiews see (a) Shostakovskii MF, Bogdanova AV (1974) The chemistry of diacetylenes. Wiley, New York, p 96

    Google Scholar 

  84. Nakayama J, Konishi T, Hoshino M (1988) Heterocycles 27:1731

    Article  CAS  Google Scholar 

  85. Gronowitz S (1985) In: Gronowitz S (ed) Heterocyclic compounds. Wiley, New York, vol 44, part 1, p 11

    Google Scholar 

  86. Schulte KE, Reich J, Walker H (1965) Chem Ber 98:98

    Article  CAS  Google Scholar 

  87. Kozhushkov SI, Haumann T, Boese R, Knieriem B, Scheib S, Bäuerle P, de Meijere A (1995) Angew Chem Int Ed Engl 34:781

    Article  CAS  Google Scholar 

  88. Hellwig J (1996) Diplomarbeit, Universität Göttingen

    Google Scholar 

  89. Since analogous macrocyclic arrays with pyrrole rings have been termed calix[n]pyrroles (cf. Gale PA, Sessler JL, Král V, Lynch V (1996) J Am Chem Soc 118:5140) it would be appropriate to rename these thiophene-crowns as calix[n]thiophenes

    Google Scholar 

  90. König B, Kozhushkov SI, de Meijere A unpublished results

    Google Scholar 

  91. König B, Rödel M, Bubenitschek P, Jones PG, Thondorf I (1995) J Org Chem 60:7406

    Article  Google Scholar 

  92. This elusive compound should be termed perspirocyclopropanecalix[6] pyrrol: cf. Sessler JL, Král V, Lynch V (1996) J Am Chem Soc 118:5140) [74]

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut für Organische Chemie der Georg-August-Universität Göttingen, Tammannstrasse 2, D-37077, Göttingen, Germany

    Armin de Meijere & Sergei I. Kozhushkov

Authors
  1. Armin de Meijere
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sergei I. Kozhushkov
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Institut für Organische Chemie, Georg-August-Universitäit, Tammannstraße 2, D-37077, Göttingen, Germany

    Armin de Meijere

Rights and permissions

Reprints and permissions

Copyright information

© 1999 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

de Meijere, A., Kozhushkov, S.I. (1999). Macrocyclic Structurally Homoconjugated Oligoacetylenes: Acetylene- and Diacetylene-Expanded Cycloalkanes and Rotanes. In: de Meijere, A. (eds) Carbon Rich Compounds II, Macrocyclic Oligoacetylenes and Other Linearly Conjugated Systems. Topics in Current Chemistry, vol 201. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-49451-0_1

Download citation

  • DOI: https://doi.org/10.1007/3-540-49451-0_1

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-65301-1

  • Online ISBN: 978-3-540-49451-5

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation