5534
D. Dondi et al. / Tetrahedron 62 (2006) 5527–5535
5. Metzger, J.; Hartmanns, J.; Koll, P. Tetrahedron Lett. 1981, 22,
1891–1894.
Anal. Calcd for C13H20O: C, 81.20, H, 10.48. Found: C,
81.0, H, 11.2.
6. (a) Fokin, A. A.; Schreiner, P. R. Adv. Synth. Catal. 2003, 345,
1035–1052; (b) Interesting results have been obtained by using
phase-transfer chemistry; See: Schreiner, P. R.; Lauenstein, O.;
Butova, E. D.; Gunchenko, P. A.; Kolomitsin, I. V.; Wittkopp,
A.; Feder, G.; Fokin, A. A. Chem. Eur. J. 2001, 7, 4996–5003;
(c) Fokin, A. A.; Schreiner, P. R. Chem. Rev. 2002, 102,
1551–1594; (d) Albini, A.; Fagnoni, M. Chim. Oggi. 2005,
22, 36–38.
5.2.15. 3-Cyclohexylmethyl-bicyclo[2.2.1]heptan-2-one
(3bm).42 Method A: 10 mL (90 mmol, 3 M) of 1b, 280 mL
(2.3 mmol, 0.08 M) of 2m, and 440 mg of xanthone
(2.3 mmol, 0.08 M) were dissolved in 20 mL of DMC. The
solution was irradiated for 20 h and 380 mg of 3bm (80%)
were formed as a colorless syrup.
7. (a) Cardarelli, A. M.; Fagnoni, M.; Mella, M.; Albini, A.
J. Org. Chem. 2001, 66, 7320–7327; (b) Campari, G.; Mella,
M.; Fagnoni, M.; Albini, A. Tetrahedron: Asymmetry 2000,
11, 1891–1906; (c) Gonzalez-Cameno, A. M.; Mella, M.;
Fagnoni, M.; Albini, A. J. Org. Chem. 2000, 65, 297–303.
8. Doohan, R. A.; Geraghty, N. W. A. Green Chem. 2005, 7, 91–96.
9. Manfrotto, C.; Mella, M.; Freccero, M.; Fagnoni, M.; Albini,
A. J. Org. Chem. 1999, 64, 5024–5028; Fraser-Reid, B.;
Anderson, R. C.; Hisks, D. R.; Walker, D. L. Can. J. Chem.
1977, 55, 3986–3995.
Method B: A solution of 1.2 mL (12 mmol, 0.5 M) of
1b, 280 mL (2.4 mmol) of 2m, and 160 mg of TBADT in
22 mL of acetonitrile was irradiated for 16 h giving
240 mg (49%) of 3bm.
The spectroscopic data of compound 3bm were in accor-
dance with literature data.42 MS (m/z) 206 (M+, 15), 110
(32), 82 (100), 67 (46), 55 (28), 41 (27). Anal. Calcd for
C14H22O: C, 81.50, H, 10.75. Found: C, 81.7, H, 10.5.
10. Kisch, H. Adv. Photochem. 2001, 26, 93–143.
11. Dondi, D.; Fagnoni, M.; Molinari, A.; Maldotti, A.; Albini, A.
Chem. Eur. J. 2004, 10, 142–148.
12. (a) Ruhlen, J. L.; Leermakers, P. A. J. Am. Chem. Soc. 1967, 89,
4944–4948; (b) Lam, E. Y. Y.; Valentine, D.; Hammond, G. S.
J. Am. Chem. Soc. 1967, 89, 3482–3487.
5.2.16. 3-Cycloheptylmethyl-bicyclo[2.2.1]heptan-2-one
(3cm). Method A: 15 mL (0.12 mol, 4.1 M) of 1c, 280 mL
(2.3 mmol, 0.08 M) of 2m, and 440 mg of xanthone
(2.3 mmol, 0.08 M) were dissolved in 15 mL of DMC. The
solution was irradiated for 20 h and 401 mg of 3cm (80%)
were isolated as a colorless syrup.
13. Wolff, S.; Schreiber, W. L.; Smith, A. B.; Agosta, W. J. Am.
Chem. Soc. 1972, 94, 7797–7806.
14. The term ‘chemical sensitization’ has also been used for this
process, the most common case being ‘Type I’ photooxygena-
tion.
Method B: A solution of 1.4 mL (12 mmol, 0.5 M) of 1c,
280 mL (2.4 mmol) of 2m, and 160 mg of TBADT in
22 mL of acetonitrile was irradiated for 16 h giving 260 mg
(45%) of 3cm.
15. (a) Bell, J. A.; Linschitz, H. J. Am. Chem. Soc. 1963, 85, 528–
533; (b) Schuster, D. I.; Brizzolara, D. F. J. Am. Chem. Soc.
1970, 92, 4357–4365.
16. Arnaut, L. G.; Caldwell, R. A.; Elbert, J. E.; Melton, L. A. Rev.
Sci. Instrum. 1992, 63, 5381–5389.
Compound 3cm: 1H NMR (CDCl3) d 0.7–1.95 (m, 24H), 2.1
(m, 1H), 2.6 (m, 2H). 13C NMR (CDCl3) d 21.1 (CH2), 25.1
(CH2), 26.0 (CH2), 26.1 (CH2), 28.2 (CH2), 28.4 (CH2), 32.8
(CH2), 34.0 (CH2), 35.4 (CH2), 36.9 (CH2), 37.1 (CH), 38.3
(CH), 50.4 (CH), 51.5 (CH). IR (neat) n/cmꢃ1 2940, 2870,
1750, 1100. Anal. Calcd for C15H24O: C, 81.76, H, 10.98.
Found: C, 81.6, H, 10.8.
17. Schuster, D. J.; Heibel, G. E.; Caldwell, R. A.; Tang, W. Photo-
chem. Photobiol. 1990, 52, 645–648.
18. The triplet energy of 3-buten-2-one 2j has shown to be difficult
to determine but probably ranges from 250 to 294 kJ/mol; see
Garcia-Exposito, E.; Bearpark, M. J.; Ortuno, R. M.; Brancha-
dell, V.; Robb, M. A.; Wilsey, S. J. Org. Chem. 2001, 66, 8811–
8814.
Acknowledgements
19. Bonneau, R. J. Am. Chem. Soc. 1980, 102, 3816–3822.
20. The same difference had been previously observed in the
photomediated radical addition of 1,3-dioxolan-2-yl radicals
onto enones. See Ref. 21.
Partial support of this work by Murst, Rome is gratefully
acknowledged. D.D. thanks INCA for a fellowship.
21. Mosca, R.; Fagnoni, M.; Mella, M.; Albini, A. Tetrahedron
2001, 57, 10319–10328.
References and notes
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24. The reduced form of TBADT is indicated here shortly as
TBADTH . Actually the structure is W10O H+. This dispro-
ꢁ
5ꢃ
32
portionates to the starting anion and to doubly reduced
6ꢃ
W10O . See: Tanielian, C. Coord. Chem. Rev. 1998, 178–
32
180, 1165–1181.
25. Actually, as it has been shown in the literature, a mixture
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