Solvent-dependent lithium bridging in allenyl-propargyllithium reagents

Organic Letters

Volumn 2, Issue 6, 2000, Pages 783-786

  Reich, Hans J ^a   Thompson, Jennifer L ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0006068920     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol990412g     Document Type: Article

References (31)

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2. (a) Reich, H. J.; Holladay, J. E. J. Am. Chem. Soc. 1995, 117, 8470- 8471. Reich, H. J.; Holladay, J. E.; Mason, J. D.; Sikorski, W. H. J. Am. Chem. Soc. 1995, 117, 12137-12150.
3. (b) Reich, H. J.; Holladay, J. E.; Walker, T. G.; Thompson, J. L. J. Am. Chem. Soc. 1999, 121, 9769-9780. Reich, H. J.; Holladay, J. E. Angew. Chem., Int. Ed., Engl. 1996, 35, 2365- 2367.
4. (b) Reich, H. J.; Holladay, J. E.; Walker, T. G.; Thompson, J. L. J. Am. Chem. Soc. 1999, 121, 9769-9780. Reich, H. J.; Holladay, J. E. Angew. Chem., Int. Ed., Engl. 1996, 35, 2365-2367.
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14. We make no distinction between contact ion pairs (CIPs) and "covalent" organolithium reagents and use the term simply to identify lithium reagents with a C-Li contact and distinguish such species from separated ion pairs (SIPs). where there is no C-Li contact.
15. 8a-d
16. (a) Schlosser, M.; Stähle, M. Angew. Chem., Int. Ed. Engl. 1980, 19, 487-489.
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18. 9
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22. Allyllithiums can become substantially localized in nonpolar solvents or when chelation effects favor such structures: Fraenkel, G.; Martin, K. V. J. Am. Chem. Soc. 1995, 117, 10336-10344. Fraenkel, G.; Qiu, F. J. Am. Chem. Soc. 1997, 119, 3571-3579 and references therein.
23. Allyllithiums can become substantially localized in nonpolar solvents or when chelation effects favor such structures: Fraenkel, G.; Martin, K. V. J. Am. Chem. Soc. 1995, 117, 10336-10344. Fraenkel, G.; Qiu, F. J. Am. Chem. Soc. 1997, 119, 3571-3579 and references therein.
24. 1a
25. 3, 137.9 Hz).
26. C in 6-Li varied between 1376 ppb at -107°C and 716 ppb at -1°C in 4.8:3.2:1 THF-ether-pentane).
27. 1b
28. 1c There is an intermediate class of easily separated CIPs such as 7-Li, where the differences are subtle and the distinction cannot be made easily.
29. D-H)/RT).
30. Allylmagnesium chloride-TMEDA has a localized σ structure in the crystal: Marsch, M.; Harms, K.; Massa, W.; Boche, G. Angew. Chem., Int. Ed. Engl. 1987, 26, 696-697.
31. 1 fashion when tris-solvated by THF is provided by: Hoppe, I.; Marsch, M.; Harms, K.; Boche, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1995, 34, 2158-2160.