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

TY - JOUR

T1 - Radical substitution with azide

T2 - TMSN3-PhI(OAc)2 as a substitute of IN3

AU - Pedersen, Christian Marcus

AU - Marinescu, Lavinia Georgeta

AU - Bols, Mikael

PY - 2005

Y1 - 2005

N2 - 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.

AB - 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.

U2 - 10.1039/b500037h

DO - 10.1039/b500037h

M3 - Journal article

C2 - 15731868

SN - 1477-0520

VL - 3

SP - 816

EP - 822

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 5

ER -