Homolytic fragmentation of allyloxychlorocarbene

Organic Letters

Volumn 7, Issue 10, 2005, Pages 2055-2058

  Moss, Robert A ^a   Ma, Yan ^a   Fu, Xiaolin ^a   Sauers, Ronald R ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; CARBENOID; CHLORIDE; CHLORINE DERIVATIVE; HYDROCARBON; RADICAL; SOLVENT;

ALLYLIC REARRANGEMENT; ARTICLE; DECOMPOSITION; FRAGMENTATION REACTION; PHOTOLYSIS; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 19544363976     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol050668o     Document Type: Article

References (31)

1. Moss, R. A.; Zheng, F.; Fedé, J.-M.; Johnson, L. A.; Sauers, R. R. J. Am. Chem. Soc. 2004, 126, 12421.
2. Moss, R. A.; Sauers, R. R.; Zheng, F.; Fu, X.; Bally, T.; Maltsev, A. J. Am. Chem. Soc. 2004, 126, 8466.
3. Moss, R. A..; Johnson, L. A.; Merrer, D. C.; Lee, G. E., Jr. J. Am. Chem. Soc. 1999, 121, 5940.
4. (a) Moss, R. A.; Ma, Y.; Sauers, R. R..; Madni, M. J. Org. Chem. 2004, 69, 3628.
5. (b) Moss, R. A.; Fu, X.; Tian, J.; Sauers, R.; Wipf, P. Org. Lett. 2005, 7, 1371.
6. Blake, M. E.; Jones, M., Jr.; Zheng, F.; Moss, R. A. Tetrahedron Lett. 2002, 43, 3069.
7. Moss, R. A.; Ma, Y.; Zheng, F.; Sauers, R. R.; Bally, T.; Maltsev, A.; Toscano, J. P.; Showalter, B. M. J. Phys. Chem. A. 2002, 106, 12281.
8. Moss, R. A.; Ma, Y.; Sauers, R. R. J. Am. Chem. Soc. 2002, 124, 13968.
9. Moss, R. A.; Kaczmarczyk, G. M.; Johnson, L. A. Synth. Commun. 2000, 30, 3233.
10. See Supporting Information for details.
11. Graham, W. H. J. Am. Chem. Soc. 1965, 87, 4396.
12. Small quantities of allyl formate and allyl dichloromethyl ether are also observed. These result from the trapping of carbene 1 by water or HCl, respectively, and are precedented: Moss, R. A.; Ge, C.-S.; Maksimovic, L. J. Am. Chem. Soc. 1996, 118, 9792.
13. 1H NMR spectrum of 3 is described by: Tsuji, J.; Kiji, J.; Imamura, S.; Morikawa, M. J. Am. Chem. Soc. 1964, 86, 4350.
14. An authentic sample was prepared by the method of: Marson, C. M.; Grabowska, U.; Fallah, A.; Walsgrove, T.; Eggleston, D. S.; Baures, P. W. J. Org. Chem. 1994, 59, 291.
15. Compounds 2 and 3 were accompanied by ∼10% of allyl dichloromethyl ether.
16. Scheutz, R. D.; Millard, F. W. J. Org. Chem. 1959, 24, 297.
17. 2Cl of 2-un.
18. 12-pentane NMR solvents.)
19. N2′ processes contribute to the fragmentation of 1 in these solvents. Details appear in: Ma, Y. Ph.D. Dissertation, Rutgers University, New Brunswick, NJ, 2003; pp 92f.
20. - too rapidly for capture by allyl cation; only 2-un and 2-re would be expected from the heterolysis of 1.
21. Nicovitch, J. M.; Kreutter, P. H.; Wine, P. H. J. Chem. Phys. 1990, 92, 3539.
22. Karpas, Z.; Klein, F. S. Int. J. Mass Spectrom. Ion Phys. 1976, 22, 189.
23. 23b Activation energies were corrected for zero-point energy differences (ZPVE) (unscaled) and thermal effects at 298.150 K. Vibrational analyses established the nature of all stationary points as either energy minima (no imaginary frequencies) or first-order saddle points (one imaginary frequency).
24. Gaussian 03, revision B.03; Gaussian, Inc: Pittsburgh, PA, 2003. See Supporting Information for the full reference.
25. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
26. (b) Lee, C.; Yang, W.; Paar, R. G. Phys. Rev. B. 1988, 37, 785.
27. Homolysis energy was calculated as the difference between the computed energies of carbene 1 and the allyl plus COCl radicals.
28. Homolysis of 1 to allyl and COCl radicals is analogous to the cleavage of allylmethoxycarbenes to allyl and methoxycarbonyl radicals: Venneri, P. C.; Warkentin, J. J. Am. Chem. Soc. 1998, 120, 11182.
29. See also the homolysis of benzyloxymethoxycarbene (Merkley, N.; El-Saidi, M.; Warkentin, J. Can. J. Chem. 2000, 78, 356) and, more distantly,
30. the radical fragmentation of hydrazinoaminocarbenes: Cattoen, X.; Miqueu, K.; Gornitzka, H.; Bourissou, D.; Bertrand, G. J. Am. Chem. Soc. 2005, 127, 3292.
31. See Moss et al., cited in ref 11.