Activation energies for the 1,2-carbon migration of ring-fused cyclopropylchlorocarbenes

Tetrahedron Letters

Volumn 46, Issue 23, 2005, Pages 4137-4141

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

^a RUTGERS UNIVERSITY   (United States)

^b UNIVERSITY OF NEVADA   (United States)

Author keywords

Carbenes; Kinetics

Indexed keywords

CARBENE; CARBON;

ARTICLE; DIMERIZATION; ENERGY; ENTROPY; KINETICS; REACTION ANALYSIS; SUBSTITUTION REACTION; TEMPERATURE;

EID: 18844379952     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2005.03.209     Document Type: Article

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12. 7
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19. 3, δ): 20.52, 25.08, 25.12, 27.40, 49.04
20. The initial addition reaction between norbornene and ethyl diazoacetate was catalyzed by CuCN: R.R. Sauers, and P.E. Sonnet Tetrahedron 20 1964 1029
21. 3, δ): 20.40, 22.98, 28.43, 29.09, 35.87, 48.91
22. +]
23. +]
24. See: R.A. Moss, L.A. Johnson, D.C. Merrer, and G.E. Lee J. Am. Chem. Soc. 121 1999 5940 for a description of the LFP system. The 1000 W Xe monitoring lamp has since been replaced by a 150 W pulsed Xe lamp
25. 23
26. Reviews: Bonneau, R.; Liu, M. T. H. Adv. Carbene Chem., Brinker, U. H., Ed. 1998, 2, 1f
27. Ref. 1b
28. Merrer, D. C.; Moss, R. A. Adv. Carbene Chem., Brinker, U. H., Ed. 2001, 3, 53f
29. R.A. Moss, W. Liu, and K. Krogh-Jespersen J. Phys. Chem. 97 1993 13413
30. P.S. Zuev, R.S. Sheridan, T.V. Albu, D.G. Truhlar, D.A. Hrovat, and W.T. Borden Science 299 2003 867
31. R.A. Moss, R.R. Sauers, R.S. Sheridan, J. Tian, and P.S. Zuev J. Am. Chem. Soc. 126 2004 10196
32. Only minor amounts of the fragmentation or rearrangement products of the carbenes were observed in initial irradiations of matrix isolated diazirines 8 or 9, suggesting at most only minor excited state diazirine participation at low temperature. See also, note 21
33. TD B3LYP/6-31+G** calculations predict shorter wavelength absorptions for the syn conformations of carbenes 2 and 3 (488 and 489 nm, respectively), compared to the anti conformers (553 and 555 nm, respectively). Preliminary experiments suggest that irradiations at 590 nm induce selective photochemistry of the anti carbenes. Mixtures of both rearrangement and fragmentation products are observed from 2 and 3 irrespective of the irradiation wavelength, although further experiments probing whether the syn and anti conformers of the carbenes may favor different products are in progress