The trichloromethide and bromodichloromethide carbanions

Organic Letters

Volumn 11, Issue 24, 2009, Pages 5702-5704

  Moss, Robert A ^a   Zhang, Min ^a   Krogh Jespersen, Karsten ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 72849130479     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol902479x     Document Type: Article

References (22)

1. Hine, J. J. Am. Chem. Soc. 1950, 72, 2438.
2. Hine, J. Divalent Carbon; Ronald Press: New York, 1964; p 36f.
3. Hine, J.; Dowell, A. M., Jr. J. Am. Chem. Soc. 1954, 76, 2688.
4. (a) Hine, J.; Burske, N. W.; Hine, M.; Langford, P. B. J. Am. Chem. Soc. 1957, 79, 1406.
5. (b) Hine, J.; Ehrenson, S. J. J. Am. Chem. Soc. 1958, 80, 824.
6. (c) Hine, J.; Langford, P. B. J. Am. Chem. Soc. 1957, 79, 5497.
7. Moss, R. A.; Tian, J.; Sauers, R. R.; Ess, D. H.; Houk, K. N.; Krogh-Jespersen, K. J. Am. Chem. Soc. 2007, 129, 5167.
8. Details of the calculations appear in the Supporting Information. The PBE/6-311+G(d) combination of exchange-correlation functionals and basis sets has shown excellent performance for the analysis of weak carbene-solute or carbene-solvent interactions, whereas the electronic transition spectra are modeled better with the B3LYP exchange-correlation functionals. The mixed computational scheme involving TD-B3LYP/6-311+G(d) excited state calculations on PBE/6-311+G(d) optimized ground state geometries combines advantages of both approaches. For examples of previous usage, see (e.g.) ref 5 and: Moss, R. A.; Wang, L.; Weintraub, E.; Krogh-Jespersen, K. J. Phys. Chem. A 2008, 112, 4651.
9. - (f = 0.025); cf. Table 1.
10. Moss, R. A.; Tian, J.; Sauers, R. R.; Skalit, C.; Krogh-Jespersen, K. Org. Lett. 2007, 9, 4053.
11. Hine, J.; Butterworth, R.; Langford, P. B. J. Am. Chem. Soc. 1958, 80, 819.
12. Moss, R. A.; Wang, L.; Krogh-Jespersen, K. J. Am. Chem. Soc. 2009, 131, 2128.
13. Cyclopropane 3 was identified by capillary GC comparison with an authentic sample.
14. The addition of CCl2Br- to acrylonitrile is assumed to be rate determining; the closure of Michael carbanion 2 is taken to be fast.
15. Moss, R. A. Acc. Chem. Res. 1980, 13, 58.
16. Moss, R. A.; Zhang, M.; Krogh-Jespersen, K. Org. Lett. 2009, 11, 1947.
17. See Table S-2 in the Supporting Information of ref 15.
18. (a) Moss, R. A.; Tian, J. J. Am. Chem. Soc. 2005, 127, 8960.
19. (b) Moss, R. A.; Tian, J. Org. Lett. 2006, 8, 1245.
20. (c) Moss, R. A.; Tian, J. Tetrahedron Lett. 2006, 47, 3419.
21. See the Supporting Information for details of this estimate.
22. -.