Reactions of Tris(trimethylsilyl)silyl Radicals with Nitroalkanes. EPR, Kinetic, and Product Studies
Authors:
- Marco Ballestri,
- Chryssostomos Chatgilialoglu,
- Marco Lucarini,
- Gian Franco Pedulli
Abstract
The radical-initiated reaction of tris(trimethylsilyl)silane with a variety of aliphatic nitro derivatives has been investigated. This silane, which for many applications is a valid alternative to tributyltin hydride, is unable to reduce tertiary nitroalkanes to the corresponding hydrocarbons. EPR results, as well as kinetic and products studies, have shown that this “anomalous” behavior is due to the fact that the nitroxide adducts formed by addition of tris(trimethylsilyl)silyl radicals to the nitro compounds fragment preferentially at the nitrogen-oxygen bond rather than at the carbon-nitrogen bond as in the analogous tributyltin adducts. The resulting silyloxy radical, (MegSi)3SiO•, undergoes a fast rearrangement (k ≥ 107 s-1 at room temperature) with migration of a Me3Si group from silicon to oxygen to give (Me3Si)2SiOSiMe3 which adds to the nitro compound affording a secondary nitroxide adduct. The kinetics of the decay of both primary and secondary adducts to nitromethane has been studied over a wide range of temperatures. With tertiary nitroalkanes persistent aminyl radicals, RNOSi(SiMe3)3, have also been detected. © 1992, American Chemical Society. All rights reserved.
- Record ID
- UAMad3ddf824d0f451b94e3bb42b6e664b1
- Author
- Journal series
- Journal of Organic Chemistry, ISSN 0022-3263
- Issue year
- 1992
- Vol
- 57
- Pages
- 948-952
- ASJC Classification
- DOI
- DOI:10.1021/jo00029a029 Opening in a new tab
- Language
- (en) English
- Score (nominal)
- 0
- Score source
- journalList
- Publication indicators
- = 26; = 28; : 1999 = 1.322; : 2006 (2 years) = 3.790 - 2007 (5 years) =3.716
- Citation count
- 38
- Uniform Resource Identifier
- https://researchportal.amu.edu.pl/info/article/UAMad3ddf824d0f451b94e3bb42b6e664b1/
- URN
urn:amu-prod:UAMad3ddf824d0f451b94e3bb42b6e664b1
* presented citation count is obtained through Internet information analysis and it is close to the number calculated by the Publish or PerishOpening in a new tab system.