Carboxylation of Alkyl Iodides with [¹¹C] and (¹³C)Carbon Monoxide: Using Sulfoxides as Oxygen Nucleophiles

Abstract

¹¹C-Labeled carboxylic acids were prepared from alkyl iodides and [¹¹C]carbon monoxide by irradiation by UV light in anhydrous DMSO solutions in the presence of triethylamine. Sulf­oxides other than DMSO can be used and may be used in stoichiometric amounts using inert solvents.

Key words

sulfoxides - radical reactions - carbonylations - carboxylic acid - photochemistry

References

• 1 Långström B. Kihlberg T. Bergström M. Antoni G. Björkman M. Forngren BH. Forngren T. Hartvig P. Markides K. Yngve U. Ögren M. Acta Chem. Scand.  1999,  53:  651 
• 2 Principles of Nuclear Medicine   2nd ed.:  Wagner HNJ. Szabo Z. Buchanan JW. W. B. Saunders Co.; Philadelphia: 1995. 
• 3 Positron Emission Tomography. Basic Science and Clinical Practice   Bailey BL. Townsend DW. Valk PE. Maisey MN. Springer-Verlag; London: 2003. 
• 4 PET for Drug Development and Evaluation   Comar D. Kluwer Academic Publishers; Dordrecht: 1995. 
• 5a Doi H. Barletta J. Suzuki M. Noyori R. Watanabe Y. Långström B. Org. Biomol. Chem.  2004,  2:  3063 
• 5b Rahman O. Kihlberg T. Långström B. Org. Biomol. Chem.  2004,  2:  1621 
• 5c Karimi F. Barletta J. Långström B. Eur. J. Org. Chem.  2005,  2374 ; and references cited therein
• 6a Långström B. Bergson G. Radiochem. Radioanal. Lett.  1980,  43:  47 
• 6b Långström B. Obenius U. Sjöberg S. Bergson G. J. Radioanal. Chem.  1981,  64:  279 
• 7a Långström B. Bergson G. Radiochem. Radioanal. Lett.  1980,  43:  47 
• 7b Långström B. Obenius U. Sjöberg S. Bergson G. J. Radioanal. Chem.  1981,  64:  279 
• 8a Kawashima H. Yajima K. Kuge Y. Hashimoto N. Miyake Y. J. Labelled Compd. Radiopharm.  1997,  39:  181 
• 8b Yajima K. Kawashima H. Hashimoto N. Miyake Y. J. Phys. Chem.  1996,  100:  14936 
• 9a Chatgilialoglu C. Crich D. Komatsu M. Ryu I. Chem. Rev.  1999,  99:  1991 
• 9b Ryu I. Chem. Soc. Rev.  2001,  16 
• 9c Ryu I. Miyazato H. Kuriyama H. Matsu K. Tojino M. Fukuyama T. Minakata S. Komatsu M. J. Am. Chem. Soc.  2003,  125:  5632 
• 9d Nagahara K. Ryu I. Komatsu M. Sonoda N. J. Am. Chem. Soc.  1997,  119:  5465 
• 9e Sugiura M. Hiroyuki H. Kobayashi S. Chem. Lett.  2003,  32:  898 
• 9f Ryu I. Nagahara K. Kambe N. Sonoda N. Kreimerman S. Komatsu M. Chem. Commun.  1998,  1953 
• 10a Itsenko O. Kihlberg T. Långström B. J. Org. Chem.  2004,  69:  4356 
• 10b Itsenko O. Långström B. J. Org. Chem.  2005,  70:  2244 
• 12a Bordwell FG. Pitt BM. J. Am. Chem. Soc.  1955,  77:  572 
• 12b Ray SK. Shaw R. Smith BC. Nature (London)  1962,  196:  372 
• 12c Amonoo-Neizer EH. Ray SK. Shaw RA. Smith BC. J. Chem. Soc.  1965,  6250 
• 12d Cocivera M. Malatesa V. Woo KW. Effio A. J. Org. Chem.  1978,  43:  1140 
• 12e Thea S. Cevasco G. J. Org. Chem.  1988,  53:  4121 
• 13 Without triethylamine the radiochemical yields of acids were less than 3%. In a related reaction of acetyl chloride with DMSO the proton transfer from the S-methyl group in the intermediate acyloxysulfonium salt has been identified as the rate-limiting step (ref. 12c); hence, triethylamine, as a base, may facilitate this step. The effect of tertiary amines in photoinitiated carbonylation using [¹¹C]carbon monoxide and other oxygen nucleophiles (water and alcohols) in comparison with several sensitizers is briefly discussed in Itsenko O. Långström B. Org. Lett.  2005,  7:  4661 
• 15 Kihlberg T, Itsenko O, Ferm T, and Långström B. inventors; PCT Int. Appl.  WO2005042441.  ; Chem. Abstr. , 142, 463193

11

Typically, [¹¹C]carbon monoxide is available in submicromolar amounts, whereas other reactants may be used on a submillimolar scale.

14

The yield was calculated from (¹³C)carbon monoxide, the reaction conditions were not optimized.