Configurational stability and stereospecificity in the reactions of amide-stabilised organolithiums: A non-stereospecific tin-lithium exchange

Tetrahedron Letters

Volumn 38, Issue 14, 1997, Pages 2565-2568

  Clayden, Jonathan ^a   Pink, Jennifer H ^a  

^a UNIVERSITY OF MANCHESTER   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOLITHIUM COMPOUND;

ARTICLE; DIASTEREOISOMER; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY; STEREOSPECIFICITY;

EID: 0030942369     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00402-4     Document Type: Article

References (25)

1. Hoffmann R.W., Julius M., Chemla F., Ruhland T., Frenzen G. Tetrahedron. 50:1994;6049.
2. Hoffmann, R.W.; Rühl, T.; Harbach, J. Liebigs Ann. Chem. 1992, 725.
3. Aggarwal V.K. Angew. Chem., Int. Ed. Engl. 33:1994;175.
4. Derwing, C.; Hoppe, D. Synthesis 1996, 149.
5. Park Y.S., Boys M.L., Beak P. J. Am. Chem. Soc. 118:1996;3757.
6. Gawley R.E., Zhang Q. J. Am. Chem. Soc. 115:1993;7515.
7. Gawley R.E., Zhang Q. Tetrahedron. 50:1994;6077.
8. Pearson W.H., Lindbeck A.C., Kampf J.W. J. Am. Chem. Soc. 115:1993;2622.
9. Hoffmann, R.W.; Rühl, T.; Chemla, F.; Zahneisen, T. Liebigs Ann. Chem. 1992, 719.
10. Thayumanavan S., Lee S., Liu C., Beak P. J. Am. Chem. Soc. 116:1994;9755.
11. Meyers A.I., Guiles J., Warmus J.S., Gonzales M.A. Tetrahedron Lett. 32:1991;5505.
12. Beak P., Du H. J. Am. Chem. Soc. 115:1993;2516.
13. Basu A., Beak P. J. Am. Chem. Soc. 118:1996;1575.
14. Basu, A.; Gallagher, D.J.; Beak, P. J. Org. Chem. 1996, 5718.
15. Still W.C., Sreekumar C. J. Am. Chem. Soc. 102:1980;1201.
16. Beak P., Basu A., Gallagher D.J., Park Y.S., Thayumanavan S. Acc. Chem. Res. 29:1996;552.
17. Carstens A., Hoppe D. Tetrahedron. 50:1994;6097.
18. Reich H.J., Borst J.P., Coplien M.B., Phillips N.H. J. Am. Chem. Soc. 114:1992;6577.
19. Clayden, J.; Pink, J.H. previous paper.
20. For other examples in which stereochemical sense depends on the electrophile see 4, 7, 16 and 17.
21. See for a similar loss of stereospecficity.
22. Provided, of course, that this transmetallation proceeds with 100% retention and not 100% inversion.
23. All of 4b was deuterated, but only a quarter of 4a. Undeuterated 4a must arise from stereospecific alkylation of undeuterated 3a derived from 5a de-deuterated syn to oxygen, while all of the 5b in the starting material is converted stereospecifically into d-4a. The remaining deuterated material (all of the 20% d-4b and half of the 20% d-4a) must then come from the d-3b produced by inhabitual anti selective (due to the kinetic isotope effect) deprotonation of 5a and provides further evidence that the alkylation reactions of 3b have only 65% stereospecificity.
24. D have been used to direct the stereochemical outcome of a reaction: see Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem., Int. Ed. Engl. 1993, 32, 394.
25. Kopach M.E., Meyers A.I. J. Org. Chem. 61:1996;6764.