Carbon tunneling in the ring expansion of noradamantylchlorocarbene

Journal of the American Chemical Society

Volumn 126, Issue 33, 2004, Pages 10196-10197

  Moss, Robert A ^a   Sauers, Ronald R ^a   Sheridan, Robert S ^b   Tian, Jingzhi ^a   Zuev, Peter S ^b  

^a RUTGERS UNIVERSITY   (United States)

^b UNIVERSITY OF NEVADA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,2 DICHLOROETHANE; ADAMANTANE DERIVATIVE; AZIRINE DERIVATIVE; CARBENOID; CARBON; CHLORINE DERIVATIVE; NORADAMANTYLCHLOROCARBENE; PYRIDINE; UNCLASSIFIED DRUG;

ABSORPTION SPECTROSCOPY; ARTICLE; INFRARED SPECTROSCOPY; LOW TEMPERATURE; PHOTOLYSIS; QUANTUM MECHANICS; REACTION ANALYSIS; SYNTHESIS;

EID: 4143089268     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0488939     Document Type: Article

References (21)

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5. Review: Merrer, D. C.; Moss, R. A. In Advances in Carbene Chemistry; Brinker, U. H., Ed.; Amsterdam: Elsevier: 2001; Vol. 3, pp 53f.
6. Zuev, P. S.; Sheridan, R. S.; Albu, T. V.; TruhIar, D. G.; Hrovat, D. A.; Borden, W. T. Science 2003, 299, 867.
7. In contrast, calculations indicate that carbon tunneling is unimportant in ring expansions of cyclopropylhalocarbenes. See: 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.
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11. Yao, G.; Rempala, P.; Bashore, C.; Sheridan, R. S. Tetrahedron Lett. 1999, 40, 17, and unpublished work.
12. Details of synthetic procedures and characterizations appear in the Supporting Information.
13. Gielen, H.; Alonso-Alija, C.; Hendrix, M.; Niewöhner, U.; Schauss, D. Tetrahedron Lett. 2002, 43, 419.
14. Graham, W. H. J. Am. Chem. Soc. 1965, 87, 4396.
15. For a description of the LFP installation, see: Moss, R. A.; Johnson, L. A.; Merrer, D. C.; Lee, G. E., Jr. J. Am. Chem. Soc. 1999, 121, 5940.
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17. 13C NMR spectra. All spectra are summarized in the Supporting Information.
18. Similar ene additions to strained alkenes have been observed previously: Ströter, T.; Jarosch, O.; Szeimies, G. Chem. Eur. J. 1999, 5, 1422.
19. Irradiations of matrices containing chloroadamantene 6 at 350 nm gave a new product tentatively identified as 11 based on analogy to the reported photochemistry of adamantene.
20. Only traces of adamantene 6 are observed after irradiation of 4. We estimate that only ca. 50-60% of carbene might react over a week under best conditions, due to matrix inhomogeneities.
21. 6 is also due to rapid rearrangement via tunneling.