Preparation of α-labeled aldehydes by base-catalyzed exchange reactions

Journal of Labelled Compounds and Radiopharmaceuticals

Volumn 53, Issue 8, 2010, Pages 556-558

  Ariza, Xavier ^a   Asins, Guillermina ^a   Garcia, Jordi ^a   Hegardt, Fausto G ^a   Makowski, Kamil ^a   Serra, Dolors ^a   Velascoa, Javier ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

Base catalysed exchange; Deuteration; Enolization; Tritiation

Indexed keywords

CATALYSIS;

BASE CATALYZED; BASE-CATALYZED EXCHANGE; DEUTERATIONS; DIMETHYLAMINO PYRIDINE; EFFICIENT PROTOCOLS; ENOLIZATION; EXCHANGE REACTION; H-D EXCHANGE; SIMPLE++; TRITIATION;

ALDEHYDES;

4 (N,N DIMETHYLAMINO)PYRIDINE; ALDEHYDE; BASE; DEUTERIUM OXIDE; PYRIDINE DERIVATIVE; TRIETHYLAMINE; TRITIUM; UNCLASSIFIED DRUG;

ALKALINITY; ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION KINETICS; DEUTERIUM HYDROGEN EXCHANGE; ISOTOPE LABELING; QUANTUM YIELD;

EID: 77956585455     PISSN: 03624803     EISSN: 10991344     Source Type: Journal    
DOI: 10.1002/jlcr.1759     Document Type: Article

References (18)

1. P. Mera, A. Bentebibel, E. López-Viñas, A. G. Cordente, C. Gurunathan, D. Sebastián, I. Vázquez, L. Herrero, X. Ariza, P. Gómez-Puertas, G. Asins, D. Serra, J. Garcia, F. G. Hegardt, Biochem. Pharmacol. 2009, 77, 1084-1095.
2. More than a hundred citations can be found in the literature on the biological activity of C75 in recent years. For very recent references, see: (a) C. Rae, A. Graham, Diabetes Obes. Metab. 2008, 10, 1271-1274;
3. (b) A. L. Cerrone-Szakal, N. A. Siegfried, P. C. Bevilacqua, J. Am. Chem. Soc. 2008, 130, 14504-14520. See also Reference 1.
4. F. P. Kuhajda, E. S. Pizer, J. N. Li, N. S. Mani, G. L. Frehywot, C. A. Townsend, Proc. Natl. Acad. Sci. U.S.A. 2000, 97, 3450-3454.
5. For a review on tritium labeling of organic compounds, see: M. Saljoughian, Synthesis 2002, 1781-1801.
6. (a) S. Buksha, G. S. Coumbarides, M. Dingjan, J. Eames, M. J. Suggate, N. Weerasooriya, J. Label. Radiopharm. 2006, 49, 757-771 and references therein;
7. (b) C. Grison, S. Petek, P. Coutrot, Tetrahedron 2005, 61, 7193-7200;
8. (c) For a very recent review on H/D exchange, see: J. Atzrodt, V. Derdau, T. Fey, J. Zimmermann, Angew. Chem. Int. Ed. 2007, 46, 7744-7765;
9. (d) See also: A. Shulman, D. Sitry, H. Shulman, E. Keinan, Chem. Eur. J. 2002, 229-239.
10. (a) G. N. Reddy, C. J. Soares, M. J. Kurth, H. J. Segall, J. Label. Radiopharm. 1991, 29, 1257-1260;
11. (b) S. B. Farren, E. Sommerman, P. R. Cullis, Chem. Phys. Lipids 1984, 34, 279-286;
12. (c) W. Kirmse, H.-D. von Scholz, H. Arold, Justus Liebigs Ann. Chem. 1968, 711, 22-30.
13. 3N and 4-DMAP show a similar pKa (∼9.1), see: (a) F. G. Bordwell, Acc. Chem. Res. 1988, 21, 456-463. See also;
14. (b) M. B. Smith, J. March, in Advanced Organic Chemistry, 5th edn., Wiley-Interscience, New York, 2001, pp. 327-362. However, an attempt at deuteration using NaCN (pKa HCN = 9.2) failed, and most of the aldehyde decomposed.
15. 2O would lead to >98% of deuterium incorporation if is needed.
16. Almost complete transformation of nonanal into self-condensation products was observed when the mixture of the aldehyde and deuterated water was heated to 100°C for 24 h.
17. The existence of an important third-order term for the catalysis of the enolisation of aldehydes has been demonstrated. See: A. F. Hegarty, J. Dowling, J. Chem. Soc., Chem. Commun. 1991, 996-997. It has been argued that this third-order term is due to an alternative, concerted mechanism of enolisation in which both, a base and its conjugated acid play a role.
18. 3N, probably due to its volatility.