Self-terminating radical oxygenations: Probing of the scope of the concept by use of various organic O-centered radicals

European Journal of Organic Chemistry

Volumn , Issue 16, 2003, Pages 3173-3178

  Jargstorff, C ^a   Wille, Uta ^b  

^a UNIVERSITY OF KIEL   (Germany)

^b UNIVERSITY OF MELBOURNE   (Australia)

Author keywords

Alkynes; Cyclizations; Oxygenations; Radical reactions; Synthetic methods

Indexed keywords

(CARBAMOYL)OXYL RADICAL; (CARBONYL)OXYL RADICAL; ALKYNE; CARBON; CARBONYL DERIVATIVE; NITROGEN; NITROXYL RADICAL; ORGANIC COMPOUND; OXYGEN; RADICAL; UNCLASSIFIED DRUG; [(CARBONYL)ACYL]OXYL RADICAL;

ARTICLE; COVALENT BOND; CYCLIZATION; OXIDATION; OXYGENATION; RADICAL REACTION; SELF TERMINATING RADICAL OXYGENATION; SYNTHESIS; TRIPLE BOND;

EID: 0041977103     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200300257     Document Type: Article

References (56)

1. J. Hartung, E. Suárez, M. S. Rodriguez, J. Boukouvalas, R. K. Haynes, in: Radicals in Organic Synthesis, Vol. 2: Applications (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim (Germany), 2001, chapter 5.
2. J. Hartung, T. Gottwald, K. Špehar, Synthesis 2002, 1469-1498; and cited refs.
3. J. Hartung, Eur. J. Org. Chem. 2001, 619-632; and cited refs.
4. C. Walling, R. T. Clark, J. Am. Chem. Soc. 1974, 96, 4530-4534.
5. C. Walling, G. El-Taliawi, J. Am. Chem. Soc. 1973, 95, 848-850.
6. S. Bottle, W. K. Busfield, I. D. Jenkins, B. W. Skelton, A. H. White, E. Rizzardo, D. H. Solomon, J. Chem. Soc., Perkin Trans. 2 1991, 1001-1007.
7. U. Wille, Chem. Eur. J. 2002, 8, 340-347.
8. Correctly, taking both possible directions of enumeration in the carbocyclic ring into account, the transannular 1,5-HAT 2 → 3a in Scheme 1 should be regarded as a 1.5/1,7-HAT. For the sake of clarity, the nomenclature for these transannular radical reactions is based on the most probable process, e.g. 1,5- or 1,6-HAT, respectively; see: J. Fossey, D. Lefort, J. Sorba, Free Radicals in Organic Chemistry, Masson, Paris, 1995.
9. U. Wille, C. Plath, Liebigs Ann./Recueil 1997, 111-119.
10. U. Wille, L. Lietzau, Tetrahedron 1999, 55, 10119-10134.
11. L. Lietzau, U. Wille, Heterocycles 2001, 55, 377-380.
12. U. Wille, Org. Lett. 2000, 2, 3485-3488.
13. U. Wille, Tetrahedron Lett. 2002, 43, 1239-1242.
14. U. Wille, J. Am. Chem. Soc. 2002, 124, 14-15.
15. U. Wille, C. Jargstorff, J. Chem. Soc., Perkin Trans. 1 2002, 1036-1041.
16. [7]
17. [9-14]
18. We have recently shown that (alkoxycarbonyl)oxyl radicals, [(alkoxycarbonyl)acyl]oxyl radicals, and alkoxyl radicals induce a similar self-terminating, oxidative radical cyclization upon addition to C≡C triple bonds in medium-sized cycloalkynones; see ref. In contrast to the reaction presented in this work, the initial radical addition is followed by a transannular cyclization to the carbonyl double bond.
19. J. Chateauneuf, J. Lusztyk, B. Maillard, K. U. Ingold, J. Am. Chem. Soc 1988, 110, 6727-6731.
20. D. J. Edge, J. K. Kochi, J. Am. Chem. Soc. 1973, 95, 2635-2643.
21. H. G. Korth, J. Chateauneuf, J. Lusztyk, K. U. Ingold, J. Am. Chem. Soc. 1988, 110, 5929-5931.
22. A. L. J. Beckwith, B. P. Hay, J. Am. Chem. Soc. 1988, 110, 4415-4416.
23. A. L. J. Beckwith, B. P. Hay, J. Am. Chem. Soc. 1989, 111, 230-234.
24. D. E. Van Sickle, J. Org. Chem. 1969, 34, 3446-3451.
25. To the best of our knowledge, absolute rate data for these processes were not determined.
26. H. Togo, M. Fuji, M. Yokoyama, Bull. Chem. Soc., Jpn. 1991, 64, 57-67.
27. G. Bucher, M. Halupka, C. Kolano, O. Schade, W. Sander, Eur. J. Org. Chem. 2001, 545-552.
28. D. H. R. Barton, D. Crich, J. Chem. Soc., Perkin Trans. 1 1986, 1603-1611.
29. P. A. Simakov, F. N. Martinez, J. H. Horner, M. Newcomb, J. Org. Chem. 1998, 63, 1226-1232.
30. M. Newcomb, M. U. Kumar, J. Boivin, E. Crépon, S. Z. Zard, Tetrahedron Lett. 1991, 32, 45-48.
31. O. M. Musa, J. H. Horner, H. Shahin, M. Newcomb, J. Am. Chem. Soc. 1996, 118, 3862-3868.
32. W. C. Danen, C. T. West, T. T. Kensler, J. Am. Chem. Soc. 1973, 95, 5716-5724.
33. J. L. Esker, M. Newcomb, J. Org. Chem. 1994, 59, 2779-2786.
34. D. Burdi, B. M. Aveline, P. D. Wood, J. Stubbe, R. W. Redmond, J. Am. Chem. Soc. 1997, 119, 6457-6460.
35. H. J. Hageman, P. Oosterhoff, T. Overeem, J. Verbeek, J. Photochem. Photobiol. A: Chemistry 1997, 110, 17-21.
36. A. C. Albéniz, P. Espinet, R. López-Fernández, A. Sen, J. Am. Chem. Soc. 2002, 124, 11278-11279.
37. D. Benoit, V. Chaplinski, R. Braslau, C. J. Hawker, J. Am. Chem. Soc. 1999, 121, 3904-3920.
38. C. Ollivier, P. Renaud, Angew. Chem. 2000, 112, 946-949; Angew. Chem. Int. Ed. 2000, 39, 925-928.
39. C. Ollivier, P. Renaud, Angew. Chem. 2000, 112, 946-949; Angew. Chem. Int. Ed. 2000, 39, 925-928.
40. P. F. Alewood, S. A. Hussain, T. C. Jenkins, M. J. Perkins, J. Chem. Soc., Perkin Trans. 1 1978, 1066-1076.
41. R. V. Hoffman, N. K. Nayyar, J. Org. Chem. 1994, 59, 3530-3539.
42. [9]
43. It was reported that the photoproducts arising from photolysis of thiazolethiones undergo complicated chemistry: W. Adam, J. Hartung, H. Okamoto, S. Marquardt, W. M. Nau, U. Pischel, C. R. Saha-Möller, K. Špehar, J. Org. Chem. 2002, 67; 6041-6049.
44. 19]
45. Although the thiazolethiones 10 were not ideal radical precursors for our purposes (see text), they were very suitable for mechanistic studies, because their reduced sensitivity towards light simplified their handling significantly.
46. [(Aryloxycarbonyl)acyl]oxyl radicals are convenient precursors for O-centered phenoxyl radicals generated through stepwise decarboxylation-decarbonylation: [45a] P. M. Lahti, D. A. Modarelli, F. C. Rossitto, A. L. Inceli, A. S. Ichimura, S. Ivatury, J. Org. Chem. 1996, 61, 1730-1738.
47. [45b] D. A. Modarelli, F. C. Rossito, P. M. Lahti, Tetrahedron Lett. 1989, 30, 4477-4480. To the best of our knowledge, no similar process has yet been described for [(alkoxycarbonyl)acyl]oxyl radicals.
48. R. Braslau, J. Org. Chem. 1995, 60, 6191-6193.
49. F. R. Stermitz, D. W. Neiswander, J. Am. Chem. Soc. 1973, 95, 2630-2634.
50. GC-MS analysis showed that small amounts of trans-6 and, presumably, trans-5 were also formed in the reactions between the nitroxyl radicals and 1. It is believed that these compounds result from subsequent acid-catalyzed isomerization of 5 and 6, since the CAN-mediated oxidation of hydroxylamines in acetonitrile is accompanied by production of equimolar amounts of protons.
51. [9,11]
52. It was verified that no reaction between 1 and the hydroxylamines 12a-d occurred in the absence of oxidant.
53. [9]
54. This is a plausible assumption, since the rate constants for hydrogen abstractions by nitroxyl radicals and addition to π-systems are of the same order of magnitude: K. U. Ingold, J. C. Walton, Landolf-Börnstein, Numerical Data and Functional Relationships in Science and Technology, Group II: Atomic and Molecular Physics, Vol. 18, Suppl. to II/13, Nitrogen-Centered Radicals, Aminoxyl and Related Radicals (Ed.: H. Fischer), Springer Verlag, Berlin, Heidelberg, New York, London, Paris, Tokyo, Hong Kong, Barcelona, Budapest, 1994, p. 400, 520.
55. Nitroxyl radical-mediated oxidation of alkynes to α,β-acetylenic ketones in the presence of oxygen has been reported in the literature: S. Sakaguchi, T. Takase, T. Iwahama, Y. Ishii, Chem. Commun. 1998, 2037-2038.
56. We have indications that the other major product formed in the reactions between 13b-d and 1 was an adduct species, possibly resulting from recombination of the nitroxyl radical and the cycloalkyne radical 18.