Iodonium Metathesis Reactions†
Takahito Kasahara
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorYoung Jin Jang
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorLéanne Racicot
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorDimitrios Panagopoulos
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorDr. Steven H. Liang
Department of Radiology, Harvard Medical School and Division of Nuclear Medicine and Medical Imaging, Massachusetts General Hospital, 55 Fruit Street, Boston, MA 02114 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Marco A. Ciufolini
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)Search for more papers by this authorTakahito Kasahara
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorYoung Jin Jang
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorLéanne Racicot
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorDimitrios Panagopoulos
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Search for more papers by this authorDr. Steven H. Liang
Department of Radiology, Harvard Medical School and Division of Nuclear Medicine and Medical Imaging, Massachusetts General Hospital, 55 Fruit Street, Boston, MA 02114 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. Marco A. Ciufolini
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1 (Canada)Search for more papers by this authorWe thank the University of British Columbia, the Canada Research Chair Program, NSERC, CFI, and BCKDF for support. T.K. is a recipient of a UBC FYF Fellowship; L.R., of a Vanier Fellowship; D.P., of an Onassis Foundation Scholarship.
Abstract
A metathesis reaction occurs when a diaryliodonium triflate is heated with an aryl iodide, resulting in the formation of a new diaryliodonium triflate.
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References
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- 9Two examples are provided as Supporting Information.
- 10The diaryliodonium triflates employed in this study were prepared as described by: M. Bielawski, M. Zhu, B. Olofsson, Adv. Synth. Catal. 2007, 349, 2610, and recrystallized before use (see the Supporting Information for details).
- 11
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- 13Diaryliodonium species with two electron-rich aryls were less reactive. Thus, the reaction of bis(4-anisyl)iodonium triflate with 4-iodotoluene went to only 65 % conversion after 16 h to give a 1.6:2.0:1.0 mixture of starting complex, 4-anisyl-4-tolyliodonium triflate, and bis-4-tolyliodonium triflate. Therefore, no further work was done with such electron-rich complexes.
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- 15The geometric mean better reflects the “true” value (the actual (+)-charge on the I atom) toward which a set of numbers (calculated charges) tend: P. J. Fleming, J. J. Wallace, Commun. ACM 1986, 29, 218.
- 16MNDO, MNDO-d, AM1, PM3 as provided in the Hyperchem package.
- 17This finds support in semiempirical calculations (see the Supporting Information), which, however, tend to be imprecise for hypervalent halogen compounds (e.g. J. J. P. Stewart, J. Comput. Chem. 1989, 10, 221). Calculated values should only be taken for reflecting a trend.
- 18The significance of this reaction derives from the fact that aryl(5-uridinyl)iodonium complexes are precursors of 5-18F-uridine, which is of considerable interest in PET imaging: Ref. [14] as well as M. S. Yusubov, D. V. Svitich, M. S. Larkina, V. V. Zhdankin, ARKIVOC 2013, 364.
- 19Iodouridine triacetate was computationally modeled with the structurally simpler 5-iodo-1-methyluracil.
- 20Metathesis also failed with highly electron-rich aryl iodides such as 4-iodoveratrole, N-(4-iodophenyl)phthalimide, and N,N-dimethyl-4-iodo-aniline, which upon contact with diaryliodonium complexes developed blue-green colors and yielded intractable mixtures of products, perhaps due to the occurrence of competing single-electron transfer (SET) processes.
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