Synthesis of a new, C2 symmetric α,α' - bis-(carboxymethyl) substituted nitroxide

Synthetic Communications

Volumn 30, Issue 10, 2000, Pages 1837-1848

  Einhorn, Jacques ^a   Einhorn, Cathy ^a   Ratajczak, Fabien ^a   Pierre, Jean Louis ^a  

^a UNIVERSITÉ JOSEPH FOURIER   (France)

Author keywords

[No Author keywords available]

Indexed keywords

NITROXIDE DERIVATIVE; PYRROLIDINE DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034051629     PISSN: 00397911     EISSN: None     Source Type: Journal    
DOI: 10.1080/00397910008087229     Document Type: Article

References (19)

1. For a general review on the synthesis and applications of optically active nitroxides, see: (a) Naik, N.; Braslau, R Tetrahedron 1998, 54, 667-696. For recent examples, see:
2. (b) Benfaremo, N., Steenbock, M.; Klapper, M.; Müllen, L; Enkelmann, V.; Cabrera, K. Liebigs Ann. 1996, 1413-1415.
3. (c) Einhorn, J.; Einhorn, C.; Ratajczak, F.; Gautier-Luneau, I.; Pierre, J.L. J. Org. Chem. 1997, 62, 9385-9388.
4. (d) Einhorn, J.; Einhorn, C.; Ratajczak, F.; Durif, A.; Averbuch, M.T.; Pierre, J.L. Tetrahedron Lett. . 1998, 39, 2565-2568.
5. (e) Rychnovsky, S.D.; Beauchamp, T.; Vaidyanathan, R.; Kwan, T. J. Org. Chem. 1998, 63, 6363-6374.
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7. (b) Rychnovsky, S.D.; Mc Lernon, T.L.; Rajapakse, H. J. Org. Chem. 1996, 61, 1194-1195.
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9. (b) Tamura, R.; Susuki, S.; Azuma, N.; Matsumoto, A.; Toda, F.; Ishii, Y. J. Org. Chem. 1995, 60, 6820-6825.
10. (a) Braslau, R.; Burrill II, L.C.; Mahal, L.K.; Wedeking, T. Angew. Chem. Int. Ed. Engl. 1997, 36, 237-238.
11. (b) Braslau, R.; Burrill II, L.C.; Chaplinski, R.H.; Papa, P.W. Tetrahedron : Asymmetry 1997, 8, 3209-3212.
12. Einhorn, J.; Einhorn, C.; Ratajczak, F.; Pierre, J.L. J. Chem. Soc., Chem. Commun. 1995, 1029-1030.
13. (a) Cignarella, G.; Nathansohn, G. J. Org. Chem. 1961, 26, 1500-1504.
14. (b) Lowe, G.; Ridley, D.D. J. Chem. Soc., Perkin Trans. I, 1973, 2024-2029.
15. 1H NMR observing the signals of their benzylic protons : they appear as a singlet in the case of the meso compound, as they are enantiotopic. In the case of the (±) compound they appear as an AB quartet, being diastereotopic.
16. Substantial amounts of 2b remained at the end of the reaction if the metallation step was performed at lower temperatures or for a shorter period.
17. 3. Effective splitting of the methyl esters singlet at 3.73 ppm was observed with racemic 4.
18. 1c Recovered 4 had an unchanged enantiomeric purity.
19. We have routinely used LDA solutions prepared from diisopropylamine, isoprene and metallic lithium in THF under ultrasonic irradiation, standardized immediately before use, see : De Nicola, A.; Einhorn, J.; Luche, J.L. J. Chem. Res. (S), 1991, 278.