Elucidation of reaction mechanisms using kinetic isotope effects of short-lived radionuclides

• Autorzy: Matsson O.
• Konferencja: Proceedings of the International Conference “2001 an Isotope Odyssey: New Application for a New Millenium", June 24-29, 2001, Zakopane, Poland
• Języki publikacji: EN

Abstrakty

EN

The use of the short-lived radionuclides 11C and 18F for the elucidation of organic reaction mechanisms is described. Examples of the different mechanistic problems that are discussed include concerted vs. stepwise base catalysed elimination (E2 or E1cB) and finding the rate limiting step for nucleophilic aromatic substitution (SNAr). The use of radionuclides to learn details about transition state structure for concerted nucleophilic aliphatic substitution (SN2) is also described.

Słowa kluczowe

EN

carbon-11; fluorine-18; kinetic isotope effect; reaction mechanism; short-lived radionuclide

• Wydawca: Institute of Nuclear Chemistry and Technology
• Czasopismo: Nukleonika
• Rocznik: 2002
• Tom: Vol. 47,suppl.1
• Strony: 43--45
• Opis fizyczny: Bibliogr. 13 poz., rys.

Twórcy

autor

Matsson O.

• Uppsala University, Institute of Chemistry, P.O. Box 531, SE-751 21 Uppsala, Sweden, Tel.: [phone], Fax: [phone],

Bibliografia

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• 4. Hill JV, Fry AJ (1962) Chlorine isotope effects in the reactions of benzyl and substituted benzyl chlorides with various nucleophiles. J Am Chem Soc 84:2763–2769
• 5. Joliot F, Curie I (1934) Artificial production of a new kind of radioelement. Nature 133:201–202
• 6. Matsson O, Axelsson S, Hussénius A, Ryberg P (1999) Mechanistic use of short-lived radionuclides in organic and bioorganic chemistry. Acta Chem Scand 53:670–679
• 7. Matsson O, Persson J, Axelsson BS, Lˆngström B, Fang Y, Westaway KC (1996) Using incoming group 11C/14C kinetic isotope effects to model the transition states for the SN2 reactions between para-substituted benzyl chlorides and labelled cyanide ion. J Am Chem Soc 118:6350–6354
• 8. Matsson O, Persson J, Axelsson S, Lˆngström B (1993) Fluorine kinetic isotope effects. J Am Chem Soc 115:5288–5289
• 9. Melander L, Saunders WH (1980) Reaction rates of isotopic molecules. Wiley Interscience, New York
• 10. Persson J, Axelsson S, Matsson O (1996) Solvent dependent leaving group fluorine kinetic isotope effect in a nucleophilic aromatic substitution reaction. J Am Chem Soc 118:20–23
• 11. Romesberg FE, Flanagan ME, Uno T, Schultz PG (1998) Mechanistic studies of an andibody-catalyzed elimination reaction. J Am Chem Soc 120:5160–5167
• 12. Ryberg P, Matsson O (2001) The mechanism of base-promoted HF elimination from 4-fluoro-4-(4’-nitrophenyl)butan-2-one: A multiple isotope effect study including the leaving group 18F/19F KIE. J Am Chem Soc 123:2712–2718
• 13. Terrier F (1991) Nucleophilic aromatic displacements: the influence of the nitro group. VCH, New York