Anatomy of a cyclohexatriene: Chemical dissection of the π and σ frame of angular [3]phenylene

Angewandte Chemie - International Edition

Volumn 43, Issue 28, 2004, Pages 3711-3715

  Kumaraswamy, Sriram ^a   Jalisatgi, Satish S ^a   Matzger, Adam J ^a   Miljanić, Ognjen Š ^a   Vollhardt, K Peter C ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Aromaticity; C C activation; Cleavage reactions; Cycloaddition; Cyclophanes

Indexed keywords

ACTIVATION ANALYSIS; BOND STRENGTH (CHEMICAL); CARBON; CHEMICAL BONDS; MOLECULAR STRUCTURE; POLYCYCLIC AROMATIC HYDROCARBONS; STEREOCHEMISTRY;

CYCLOHEXATRIENE; PARACYCLOPHANE; PHENYLENE;

OLEFINS;

ALKENE DERIVATIVE; CARBON; COBALT DERIVATIVE; CYCLOHEXATRIENE; PARACYCLOPHANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; CRYSTAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 4644292759     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200454126     Document Type: Article

References (66)

1. a) D. L. Mohler, K. P. C. Vollhardt in Advances in Strain in Organic Chemistry, Vol. 5 (Ed.: B. Halton), JAI, London, 1996, p. 121;
2. for recent references, see: b) D. Bruns, H. Miura, K. P. C. Vollhardt, Org. Lett. 2003, 5, 549;
3. c) C. Dosche, M. U. Kumke, F. Ariese, A. N. Bader, C. Gooijer, P. I. Dosa, S. Han, O. Š. Miljanić, K. P. C. Vollhardt, R. Puchta, N. J. R. van Eikema - Hommes, Phys. Chem. Chem. Phys. 2003, 5, 4563.
4. M. K. Shepherd, Cyclobutarenes. The Chemistry of Benzocyclobutene, Biphenylene, and Related Compounds, Elsevier, Amsterdam, 1991.
5. a) H. Mestdagh, K. P. C. Vollhardt, J. Chem. Soc. Chem. Commun. 1986, 281;
6. b) B. C. Berris, G. H. Hovakeemian, Y.-H. Lai, H. Mestdagh, K. P. C. Vollhardt, J. Am. Chem. Soc. 1985, 107, 5670.
7. a) H.-D. Beckhaus, R. Faust, A. J. Matzger, D. L. Mohler, D. W. Rogers, C. Rüchardt, A. K. Sawhney, S. P. Verevkin, K. P. C. Vollhardt, S. Wolff, J. Am. Chem. Soc. 2000, 122, 7819;
8. b) D. L. Mohler, K. P. C. Vollhardt, S. Wolff, Angew. Chem. 1995, 107, 601; Angew. Chem. Int. Ed. Engl. 1995, 34, 563;
9. b) D. L. Mohler, K. P. C. Vollhardt, S. Wolff, Angew. Chem. 1995, 107, 601; Angew. Chem. Int. Ed. Engl. 1995, 34, 563;
10. c) D. L. Mohler, K. P. C. Vollhardt, S. Wolff, Angew. Chem. 1990, 102, 1200; Angew. Chem. Int. Ed. Engl. 1990, 29, 1151;
11. c) D. L. Mohler, K. P. C. Vollhardt, S. Wolff, Angew. Chem. 1990, 102, 1200; Angew. Chem. Int. Ed. Engl. 1990, 29, 1151;
12. d) R. Diercks, K. P. C. Vollhardt, J. Am. Chem. Soc. 1986, 108, 3150.
13. R. Diercks, K. P. C. Vollhardt, Angew. Chem. 1986, 98, 268; Angew. Chem. Int. Ed. Engl 1986, 25, 266.
14. R. Diercks, K. P. C Vollhardt, Angew. Chem. 1986, 98, 268; Angew. Chem. Int. Ed. Engl 1986, 25, 266.
15. P. I. Dosa, A. Schleifenbaum, K. P. C. Vollhardt, Org. Lett. 2001, 3, 1017.
16. J. M. Schulman, R. L. Disch, H. Jiao, P. von R. Schleyer, J. Phys. Chem. A 1998, 102, 8051.
17. a) S. Han, D. R. Anderson, A. D. Bond, H. V. Chu, R. L. Disch, D. Holmes, J. M. Schulman, S. J. Teat, K. P. C. Vollhardt, G. D. Whitener, Angew. Chem. 2002, 114, 3361; Angew. Chem. Int. Ed. 2002, 41, 3227;
18. a) S. Han, D. R. Anderson, A. D. Bond, H. V. Chu, R. L. Disch, D. Holmes, J. M. Schulman, S. J. Teat, K. P. C. Vollhardt, G. D. Whitener, Angew. Chem. 2002, 114, 3361; Angew. Chem. Int. Ed. 2002, 41, 3227;
19. b) S. Han, A. D. Bond, R. L. Disch, D. Holmes, J. M. Schulman, S. J. Teat, K. P. C. Vollhardt, G. D. Whitener, Angew. Chem. 2002, 114, 3357; Angew. Chem. Int. Ed. 2002, 41, 3223.
20. b) S. Han, A. D. Bond, R. L. Disch, D. Holmes, J. M. Schulman, S. J. Teat, K. P. C. Vollhardt, G. D. Whitener, Angew. Chem. 2002, 114, 3357; Angew. Chem. Int. Ed. 2002, 41, 3223.
21. C. Eickmeier, D. Holmes, H. Junga, A. J. Matzger, F. Scherhag, M. Shim, K. P. C. Vollhardt, Angew. Chem. 1999, 111, 856; Angew. Chem. Int. Ed. 1999, 38, 800.
22. C. Eickmeier, D. Holmes, H. Junga, A. J. Matzger, F. Scherhag, M. Shim, K. P. C. Vollhardt, Angew. Chem. 1999, 111, 856; Angew. Chem. Int. Ed. 1999, 38, 800.
23. a) J. M. Schulman, R. L. Disch, J. Phys. Chem. A 2003, 107, 5223;
24. b) A. Rajca, A. Safronov, S. Rajca, C. R. Ross II, J. J. Stezowski, J. Am. Chem. Soc. 1996, 118, 7272;
25. c) M. Baumgarten, F. Dietz, K. Müllen, S. Karabunarliev, N. Tyutyulkov, Chem. Phys. Lett. 1994, 221, 71;
26. d) N. Trinajstic, T. G. Schmalz, T. P. Živkovic, S. Nikolić, G. E. Kite, D. J. Klein, W. A. Seitz, New J. Chem. 1991, 15, 27;
27. e) J. L. Brédas, R. H. Baughman, J. Polym. Sci. Polym. Lett. Ed. 1983, 21, 475.
28. C. Eickmeier, H. Junga, A. J. Matzger, F. Scherhag, M. Shim, K. P. C. Vollhardt, Angew. Chem. 1997, 109, 2194; Angew. Chem. Int. Ed. Engl. 1997, 36, 2103.
29. C. Eickmeier, H. Junga, A. J. Matzger, F. Scherhag, M. Shim, K. P. C. Vollhardt, Angew. Chem. 1997, 109, 2194; Angew. Chem. Int. Ed. Engl. 1997, 36, 2103.
30. W. Adam, M. Balci, H. Kiliç, J. Org. Chem. 1998, 63, 8544. The trans stereochemistry of this trioxide was assigned on mechanistic grounds, but an all-cis array could not be ruled out: M. Balci, personal communication.
31. W. Adam, M. Balci, H. Kiliç, J. Org. Chem. 1998, 63, 8544. The trans stereochemistry of this trioxide was assigned on mechanistic grounds, but an all-cis array could not be ruled out: M. Balci, personal communication.
32. All new compounds gave satisfactory analytical and/or spectral data, unless mentioned otherwise.
33. F. Sevin, M. L. McKee, J. Am. Chem. Soc. 2001, 123, 4591, and references therein.
34. A. T. Balaban, M. Banciu, V. Ciorba, Annulenes, Benzo-, Hetero-, Homo-Derivatives and Their Valence Isomers, Vol. 2, CRC, Boca Raton, FL, 1987, p. 146.
35. 2: a) B. Uno, N. Okumura, K. Seto, J. Phys. Chem. A 2000, 104, 3064;
36. 2: b) D. L. Mohler, K. P. C. Vollhardt, unpublished results; neither complex proceeds to cycloadducts.
37. 13 C NMR-Spektroskopie, Thieme, Stuttgart, 1984;
38. b) L. Knothe, H. Prinzbach, Justus Liebigs Ann. Chem. 1977, 687;
39. c) W. W. Zajac, Jr., T. R. Walters, J. Buzby, J. Gagnon, M. Labroli, Synth. Commun. 1994, 24, 427.
40. a) For cyclobutarenes, see, for example: F. Toda, P. J. Garratt, Chem. Rev. 1992, 92, 1685;
41. b) for cyclophanes, see, for example: F. Vögtle, Cyclophane Chemistry, Wiley, Chichester, 1993.
42. See: a) M. A. Battiste, J.-X. Duan, Y.-A. Zhai, I. Ghiviriga, K. A. Abboud, A. Roitberg, G. R. Shelton, W. R. Dolbier, Jr., Tetrahedron Lett. 2002, 43, 7047;
43. b) F.-G. Klärner, R. Ehrhardt, H. Bandmann, R. Boese, D. Bläser, K. N. Houk, B. R. Beno, Chem. Eur. J. 1999, 5, 2119;
44. c) H. Hopf, B. Witulski in Modern Acetylene Chemistry (Eds.: P. J. Stang, F. Diederich), VCH, Weinheim, 1995, p. 33;
45. d) E. Ciganek, Org. React. 1984, 32, 1;
46. e) I. Tabushi, H. Yamada, Z. Yoshida, R. Oda, Bull. Chem. Soc. Jpn. 1977, 50, 285;
47. f) R. S. H. Liu, C. G. Krespan, J. Org. Chem. 1969, 34, 1271, and references therein.
48. -1: H.-D. Martin, T. Urganek, R. Braun, R. Walsh, Int. J. Chem. Kinet. 1984, 16, 117; see also: M.-C. Lasne, J.-L. Ripoll, Synthesis 1985, 121.
49. -1: H.-D. Martin, T. Urganek, R. Braun, R. Walsh, Int. J. Chem. Kinet. 1984, 16, 117; see also: M.-C. Lasne, J.-L. Ripoll, Synthesis 1985, 121.
50. a) G. J. Bodwell, T. Satou, Angew. Chem. 2002, 114, 4175; Angew. Chem. Int. Ed. 2002, 41, 4003, and references therein;
51. a) G. J. Bodwell, T. Satou, Angew. Chem. 2002, 114, 4175; Angew. Chem. Int. Ed. 2002, 41, 4003, and references therein;
52. b) for the closest ethynologous analogues of 8, see: S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. 2000, 112, 393; Angew. Chem. Int. Ed. 2000, 39, 385.
53. b) for the closest ethynologous analogues of 8, see: S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. 2000, 112, 393; Angew. Chem. Int. Ed. 2000, 39, 385.
54. w = 0.030. CCDC-232267 (8) and CCDC-232268 (10) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
55. See the structure of diphenylethyne: A. A. Espiritu, J. G. White, Z. Kristallogr. 1978, 147, 177.
56. a) There appears to be only one other [6]paracyclophane structure with a higher value (44.6°): Y. Tobe, K. Ueda, T. Kaneda, K. Kakiuchi, Y. Odaira, Y. Kai, N. Kasai, J. Am. Chem. Soc. 1987, 109, 1136; see also: J. Liebe, C. Wolff, C. Krieger, J. Weiss, W. Tochtermann, Chem. Ber. 1985, 118, 4144;
57. a) There appears to be only one other [6]paracyclophane structure with a higher value (44.6°): Y. Tobe, K. Ueda, T. Kaneda, K. Kakiuchi, Y. Odaira, Y. Kai, N. Kasai, J. Am. Chem. Soc. 1987, 109, 1136; see also: J. Liebe, C. Wolff, C. Krieger, J. Weiss, W. Tochtermann, Chem. Ber. 1985, 118, 4144;
58. b) a [1.1]paracyclophane, formally a [6]paracyclophane, is even more distorted (49.8°): T. Tsuji, M. Ohkita, H. Kawai, Bull. Chem. Soc. Jpn. 2002, 75, 415, and references therein.
59. a) R. C. Haddon, J. Am. Chem. Soc. 1986, 108, 2837;
60. b) L. W. Jenneskens, E. N. van Eenige, J. N. Louwen, New J. Chem. 1992, 16, 775.
61. a) Y. Tobe, Top. Curr. Chem. 1994, 172, 1;
62. b) H. Meier in Advances in Strain in Organic Chemistry, Vol. 1 (Ed.: B. Halton), JAI, London, 1991, p. 216.
63. M. Eckert-Maksić, W. M. F. Fabian, R. Janoschek, Z. B. Maksić, J. Mol. Struct. (THEOCHEM) 1995, 338, 1.
64. See, for example: a) C. Perthuisot, B. L. Edelbach, D. L. Zubris, W. D. Jones, Organometallics 1997, 16, 2016; for a review, see: M. Oh, K. Yu, H. Li, E. J. Watson, G. B. Carpenter, D. A. Sweigart, Adv. Synth. Catal 2003, 345, 1053.
65. See, for example: a) C. Perthuisot, B. L. Edelbach, D. L. Zubris, W. D. Jones, Organometallics 1997, 16, 2016; for a review, see: M. Oh, K. Yu, H. Li, E. J. Watson, G. B. Carpenter, D. A. Sweigart, Adv. Synth. Catal 2003, 345, 1053.
66. M. Kurashina, M. Murata, T. Watanabe, H. Nishihara, J. Am. Chem. Soc. 2003, 125, 12420, and references therein.