Conformational product control in the low-temperature photochemistry of cyclopropylcarbenes

Organic Letters

Volumn 8, Issue 21, 2006, Pages 4963-4966

  Zuev, Peter S ^a   Sheridan, Robert S ^a   Sauers, Ronald R ^b   Moss, Robert A ^b   Chu, Gaosheng ^b  

^a UNIVERSITY OF NEVADA   (United States)

^b RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33750365493     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0620601     Document Type: Article

References (28)

1. (a) Kirmse, W. Carbene Chemistry; Academic Press: New York, 1972.
2. (b) Carbenes; Moss, R. A., Jones, M., Jr., Eds.; Wiley: New York, 1973; Vol. I; 1975; Vol. II.
3. For examples of calculational treatments, see, e.g.: (a) Bettinger, H. F.; Schleyer, P. v. R.; Schreiner, P. R.; Schaefer, H. F. In Modern Electronic Structure Theory and Applications in Organic Chemistry; Davidson, E. R., Ed.; World Scientific Publishing: Hackensack, NJ, 1997; p 89.
4. (b) Evanseck, J. D.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 9148.
5. (c) Sulzbach, H. M.; Platz, M. S.; Schaefer, H. F.; Hadad, C. M. J. Am. Chem. Soc. 1997, 119, 5682.
6. For leading references, see: Huang, H.; Platz, M. S. J. Am. Chem. Soc. 1998, 120, 5990.
7. (b) Platz, M. S. Adv. Carbene Chem. (Brinker, U. H., Ed.) 1998, 2, 133.
8. For theoretical examinations of cyclopropylcarbene rearrangements, see: (a) Hoffmann, R.; Zeiss, G. D.; Van Dine, G. W. J. Am. Chem. Soc. 1968, 90, 1485.
9. (b) Schoeller, W. W. J. Org. Chem. 1980, 45, 2161.
10. (c) Shevlin, P. B.; McKee, M. L. J. Am. Chem. Soc. 1989, 111, 519.
11. (d) Choa, J.-H.; McKee, M. L.; DeFelppis, J.; Squillacote, M.; Shevlin, P. B. J. Org. Chem. 1990, 55, 3291.
12. (e) Herges, R. Angew. Chem., Int. Ed. 1994, 33, 255.
13. (f) Thamattoor, D. M.; Snoonian, J. R.; Sulzbach, H. M.; Hadad, C. M. J. Org. Chem. 1999, 64, 5886.
14. (g) Muck-Lichtenfeld, C. J. Org. Chem. 2000, 65, 1366.
15. (h) Albu, T. V.; Lynch, B. J.; Truhlar, D. G.; Goren, A. C.; Hrovat, D. A.; Borden, W. T.; Moss, R. A. J. Phys. Chem. A 2002, 106, 5323.
16. Chu, G.; Moss, R. A.; Sauers, R. R.; Sheridan, R. S.; Zuev, P. S. Tetrahedron Lett. 2005, 46, 4137.
17. For a general description of the matrix isolation instrumentation, see: Sheridan, R. S.; Zuev, P. S. J. Am. Chem. Soc. 2004, 126, 12220 and references therein.
18. 9c The BH&HLYP functional with a 6-31G(d) basis set was used for enegetics and the B3LYP functional with a 6-31+G(dp) basis set was used for vibrational and TD calculations. Vibrational analyses established the nature of all stationary points as either energy minima (no imaginary frequencies) or first-order saddle points (one imaginary frequency).
19. Gaussian 03, Revision B.02; Gaussian, Inc.; Pittsburgh, PA, 2003. See the Supporting Information for the entire reference.
20. (a) Becke, A. D. J. Chem. Phys. 1992, 98, 1372.
21. (b) Miehlich, B.; Savin, A.; Stoll, H.; Pruess, H. Chem. Phys. Lett. 1989, 157, 200.
22. (c) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
23. The IR spectra of 6 and 11 were predicted by calculation and those of 7, 8, and 12 by comparison to authentic samples.
24. Matsumura, M.; Ammann, J. R.; Sheridan, R. S. Tetrahedron Lett. 1992, 33, 1843.
25. 4c have proposed that a diradical mechanism may have a lower energy transition state in the cleavage of 1.
26. 4c If similar barriers exist for excited singlet 5 and 10, rearrangement and fragmentation are likely highly efficient.
27. See, for example: (a) Khasanova, T.; Sheridan, R. S. J. Am. Chem. Soc. 1998, 120, 233.
28. (b) Khasanova, T.; Sheridan, R. S. Org. Lett. 1999, 1, 1091.