On the 6-endo selectivity in 4-penten-1-oxyl radical cyclizations

Journal of the American Chemical Society

Volumn 126, Issue 38, 2004, Pages 12121-12129

  Hartung, Jens ^a,b   Kneuer, Rainer ^a   Rummey, Christian ^a   Bringmann, Gerhard ^a  

^a UNIVERSITY OF WÜRZBURG   (Germany)

^b France   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; PROBABILITY DENSITY FUNCTION; REACTION KINETICS; STRAIN;

CARBON ATOMS; CYCLIZATIONS; REGIOSELECTIVITIES; TRANSITION STATE ENERGIES;

STEREOCHEMISTRY;

4 METHYL DERIVATIVE; 4 PENTEN 1 OXYL RADICAL; 4 PHENYL 4 PENTEN 1 OXYL RADICAL; CARBON; METHYL GROUP; RADICAL; TETRAHYDROFURAN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; CYCLIZATION; DENSITY FUNCTIONAL THEORY; GEOMETRY; MATHEMATICAL COMPUTING; MOLECULAR INTERACTION; PHASE TRANSITION; REACTION ANALYSIS; STRESS STRAIN RELATIONSHIP; STRUCTURE ANALYSIS; SUBSTITUTION REACTION;

EID: 4644298920     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049010g     Document Type: Article

References (75)

1. The following abbreviations have been applied: C = chair conformer (for tetrahydropyran-derived structures); DTA = differential thermoanalysis; E = envelope conformer (for tetrahydrofuran-derived structures); T = twist conformer (for tetrahydrofuran-derived structures); TB = twist boat conformer (for tetrahydropyran-derived structures); ZPVE = zero-point vibrational energy.
2. For the discovery of the 5-exo-trig-cyclization of 1a, see: (a) Surzur, J.-M.; Bertrand, M.-P.; Nougier, R. Tetrahedron Lett. 1969, 4197-4200.
3. For early work on the 5-exo-trig cyclization 1a-2a, see: (b) Rieke, R. D.; Moore, N. A. J. Org. Chem. 1972, 37, 413-418.
4. (c) Gilbert, B. C.; Holmes, R. G. G.; Laue, H. A. H.; Normann, R. O. C. J. Chem. Soc., Perkin Trans. 2 1976, 1047-1052.
5. (d) Beckwith, A. L. J.; Hay, B. P. J. Am. Chem. Soc. 1988, 110, 4415-4416.
6. (e) Beckwith, A. L. J.; Hay, B. P.; Williamson, G. M. J. Chem. Soc., Chem. Commun. 1989, 1202-1203.
7. For the discovery of the 6-endo-trig-mode of cyclization of the 4-penten-1-oxyl radical (1a) see: Hartung, J.; Gallou, F. J. Org. Chem. 1995, 60, 6706-6716.
8. For reviews on the 4-penten-1-oxyl radical cyclization, see: (a) Hartung, J. Eur. J. Org. Chem. 2001, 619-632.
9. (b) Hartung, J. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 2, pp 425-439.
10. (a) Hartung, J.; Hiller, M.; Schmidt, P. Chem.-Eur. J. 1996, 2, 1014-1023.
11. (b) Hartung, J.; Hiller, M.; Schmidt, P. Liebigs Ann. Chem. 1996, 1425-1436.
12. (c) Hartung, J.; Schwarz, M.; Svoboda, I.; Fuess, H. Eur. J. Org. Chem. 1999, 1275-1290.
13. Hartung, J.; Gottwald, T.; Špehar, K. Synthesis 2002, 1469-1498.
14. (a) Hartung, J.; Kneuer, R.; Laug, S.; Schmidt, P.; Spehar, K.; Svoboda, I.; Fuess, H. Eur. J. Org. Chem. 2003, 4033-4052.
15. (b) Hartung, J.; Kopf, T. M.; Kneuer, R.; Schmidt, P. C. R. Acad. Sci. Paris, Chemie/Chemistry 2001, 649-666.
16. (c) Hartung, J.; Kneuer, R. Eur. J. Org. Chem. 2000, 1677-1683.
17. Hartung, J.; Kneuer, R. Tetrahedron: Asymmetry 2003, 14, 3019-3031.
18. (a) Hartung, J.; Greb, M. Tetrahedron Lett. 2003, 44, 6091-6063.
19. (b) Jung, M. E.; Fahr, B. T.; D'Amico, D. C. J. Org. Chem. 1998, 63, 2982-2987.
20. (c) Corey, E. J.; Ha, D.-C. Tetrahedron Lett. 1988, 29, 3171-3174.
21. (d) González, A. G.; Martín, J. D.; Pérez, C.; Ramírez, M. A.; Ravelo, F. Tetrahedron Lett. 1981, 22, 5071-5072.
22. (e) Harmange, J.-C.; Figadère, B. Tetrahedron: Asymmetry 1993, 4, 1711-1754.
23. (f) Bartlett, P. A. In Asymmetric Synthesis; Morrision, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, pp 411-453.
24. Hartung, J.; Stowasser, R.; Vitt, D.; Bringmann, G. Angew. Chem. 1996, 108, 3056-3059; Angew. Chem., Int. Ed. Engl. 1996, 35, 2820-2823.
25. Hartung, J.; Stowasser, R.; Vitt, D.; Bringmann, G. Angew. Chem. 1996, 108, 3056-3059; Angew. Chem., Int. Ed. Engl. 1996, 35, 2820-2823.
26. (a) Hartung, J. In Encyclopedia for Reagents in Organic Synthesis; Crich, D., Ed.; John Wiley & Sons: New York, NY, in press.
27. (b) Hartung, J.; Schwarz, M. Org. Synth. 2002, 79, 228-235.
28. (a) Ansell, M. F.; Thomas, D. A. J. Chem. Soc. 1961, 539-542.
29. (b) Larock, R. C.; Yang, H.; Weinreb, S. M.; Herr, R. J. J. Org. Chem. 1994, 59, 4172-4178.
30. Matlin, A. R.; Clifford, C. F.; Wolff, S.; Agosta, W. C. J. Am. Chem. Soc. 1986, 108, 3385-3394.
31. Eliel, E. L.; Hargrave, K. D.; Pietrusiewicz, K. M.; Manoharan, M. J. Am. Chem. Soc. 1982, 104, 3635-3643.
32. Mihailovic, M. L.; Gojkovic, S.; Milosavljevic, S.; Konstantinovic, S. Indian J. Chem. 1999, 38B, 101-105.
33. Quantum chemical calculations were carried out on Intel LinuX Workstations using the Gaussian 98 (revision A.7) software: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
34. (a) Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724-728.
35. (b) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261.
36. (c) Hariharan, P. C.; Pople, J. A. Mol. Phys. 1974, 27, 209-214.
37. Maxwell, B. J.; Smith, B. J.; Tsanaktsidis, J. J. Chem. Soc., Perkin Trans. 2000, 425-431.
38. (a) Barckholtz, C.; Barckholtz, T. A.; Hadad, C. M. J. Phys. Chem. A 2001, 105, 140-152.
39. (b) Ricca, A.; Bauschlicher, C. W., Jr. Chem. Phys. Lett. 2000, 328, 396-402.
40. (c) Alvarez-Idaboy, J. R.; Mora-Diez, N.; Vivier-Bunge, A. J. Am. Chem. Soc. 2000, 122, 3715-3720.
41. (d) Wong, M. W.; Radom, L. J. Phys. Chem. 1995, 99, 8582-8588.
42. (a) Jursic, B. S. THEOCHEM 1999, 492, 285-291.
43. (b) Van Speybroeck, V.; Borremans, Y.; Van Neck, D.; Waroquier, M.; Wauters, S.; Saeys, M.; Marin, G. B. J. Phys. Chem. A 2001, 105, 7713-7723.
44. (c) Milet, A.; Arnaud, R. J. Org. Chem. 2001, 66, 6074-6082.
45. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
46. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1998, B37, 785-789.
47. Eyring, J. J. Chem. Phys. 1935, 3, 107-115.
48. 3: Lehmann, J. Kohlenhydrate; Thieme: Stuttgart, 1996; pp 16-37.
49. Nomenclature for twist and envelope conformers: superscripts are used for atoms which are displaced above the plane of three (T conformers) or four atoms (E conformer). Subscripts refer to atoms which are located underneath these planes. For a proper assignment of subscripts and superscripts of conformers, the atoms of the heterocyclic core, which define a plane, follow a clockwise arrangement with increasing atom count (i.e., O1-C2-C3): (a) Romers, C.; Altona, C.; Buys, H. R.; Havinga, E. Top. Stereochem. 1969, 4, 39-97.
50. (b) Zschunke, A. Molekülstruktur; Spektrum Akademischer Verlag: Heidelberg, 1993; pp 118-136.
51. Beckwith, A. L. J.; Schiesser, C. H. Tetrahedron 1985, 41, 3925-3941.
52. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902-3909.
53. This interpretation is based on results from an investigation on diastereoselective 4-tert-butyl cyclohexyl radical reactions: Damm, W.; Giese, B.; Hartung, J.; Hasskerl, T.; Houk, K. N.; Hüter, O.; Zipse, H. J. Am. Chem. Soc. 1992, 114, 4067-4079.
54. Bond, A. D.; Davies, J. E. Acta Crystallogr. 2002, E58, o331-o333.
55. Leffler, J. E. An Introduction to Free Radicals; Wiley: New York, 1993.
56. Beckwith, A. L. J.; Moad, G. J. Chem. Soc., Chem. Commun. 1974, 472-473.
57. Gottwald, T.; Greb, M.; Hartung, J. Synlett 2004, 65-68.
58. (a) Hartung, J.; Gottwald, T.; Kneuer, R. Synlett 2001, 749-752.
59. (b) Kneuer, R. Diploma Thesis, Universität Würzburg, 1996.
60. Chatgilialoglou, C. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, 2001; Vol. 1, pp 28-49.
61. The atom count changes by +1 in going from a 4-penten-1-oxyl radical (i.e., numbering of carbon atoms) to the corresponding 5-exo-trig cyclizationproduct or a tetrahydrofuran-derived transition structure, since the Hantzsch-Widman convention applies for all conformers with a heterocyclic core (i.e., oxygen has a higher priority than carbon).
62. A twist-like transition structure has recently been observed in a 5-exo-trig cyclization of an an acetal-derived alkyl radical: Corminboef, O.; Renaud, P.; Schiesser, C. H. Chem.-Eur. J. 2003, 9, 1578-1584.
63. (a) Strajbl, M.; Florián, J. Theor. Chem. Acc. 1998, 99, 166-170.
64. (b) Han, J. S.; Kang, Y. K. THEOCHEM 1996, 363, 157-165.
65. Freeman, F.; Kasner, J. A.; Kasner, M. L.; Hehre, W. J. J. THEOCHEM 2000, 496, 19-39.
66. Kirby, A. J. Stereoelectronic Effects; Oxford University Press: New York, 1996.
67. Bogner, J.; Duplan, J.-C.; Infarnet, Y.; Delmut, J.; Huet, J. Bull. Chim. Soc. Fr. 1972, 3616-3624.
68. Houk, K. N.; Paddon-Row, M. N.; Spellmeyer, D. C.; Rondan, N. G.; Nagase, S. J. Org. Chem. 1986, 51, 2874-2879.
69. Howard, J. A.; Scaiano, J. C. In Kinetische Daten von Radikal reaktionen in Lösung - Oxyl, Peroxyl und verwandte Radikale in Landolt-Börnstein, Zahlenwerte und Funktionen aus Naturwissenschaft und Technik, New Series Part D.; Fischer, H., Ed.; Springer: Berlin, 1984; Vol. 13, pp 1-127.
70. Rothenberg, G.; Sasson, Y. Tetrahedron 1998, 54, 5417-5422.
71. Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334-338.
72. (a) Bell, R. P. Proc. R. Soc. London, 1936, 154A, 414.
73. (b) Evans, M. G.; Polanyi, Trans. Faraday Soc. 1938, 34, 11.
74. Fleming, I. Grenzorbitale und Reaktionen organischer Verbindungen; Wiley-VCH: Weinheim, 1990.
75. Jones, M. J.; Moad, G.; Rizzardo, E.; Solomon, D. H. J. Org. Chem. 1989, 54, 1607-1611.