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Pedersen CM, Marinescu LG, Bols M. Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3. Org Biomol Chem. 2005;3(5):816-22doi: 10.1039/b500037h.
Pedersen, C. M., Marinescu, L. G., & Bols, M. (2005). Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3. Organic & biomolecular chemistry, 3(5), 816-22. https://doi.org/10.1039/b500037h
Pedersen, Christian Marcus, et al. "Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3." Organic & biomolecular chemistry vol. 3,5 (2005): 816-22. doi: https://doi.org/10.1039/b500037h
Pedersen CM, Marinescu LG, Bols M. Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3. Org Biomol Chem. 2005 Mar 07;3(5):816-22. doi: 10.1039/b500037h. Epub 2005 Jan 27. PMID: 15731868.
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Org Biomol Chem. 2005 Mar 07;3(5):816-22. doi: 10.1039/b500037h. Epub 2005 Jan 27.

Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of IN3.

Organic & biomolecular chemistry

Christian Marcus Pedersen, Lavinia Georgeta Marinescu, Mikael Bols

Affiliations

  1. Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000, Aarhus C, Denmark.

PMID: 15731868 DOI: 10.1039/b500037h

Abstract

TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed.

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