Silylated Cyclohexadienes as New Radical Chain Reducing Reagents: Preparative and Mechanistic Aspects

A Studer, S Amrein, F Schleth, T Schulte, John Christopher Walton

Research output: Contribution to journalArticlepeer-review

75 Citations (Scopus)

Abstract

Various silylated 1,4-cyclohexadienes are presented as superior tin hydride substitutes for the conduction of various radical chain reductions. Debrominations, deiodinations, and deselenations can be performed using these environmentally benign reagents. Furthermore, Barton-McCombie-type deoxygenations using silylated cyclohexadienes are described. Radical cyclizations, ring expansions, and Giese-type addition reactions with the new tin hydride substitutes are presented. The polymerization of styrene can be regulated using silylated cyclohexadienes. Rate constants for hydrogen atom abstraction from two 1-silyl-cyclohexadienes by primary C-radicals were determined. The effects of the cyclohexadiene substituents on the reaction outcomes are discussed. Finally, qualitative EPR experiments on silyl radical expulsion from silylated cyclohexadienyl radicals are presented.

Original languageEnglish
Pages (from-to)5726-5733
Number of pages8
JournalJournal of the American Chemical Society
Volume125
Issue number19
DOIs
Publication statusPublished - 14 May 2003

Keywords

  • NORMAL-BUTYLTIN HYDRIDE
  • ELECTRON-SPIN-RESONANCE
  • ABSOLUTE RATE CONSTANTS
  • BETA-KETO-ESTERS
  • ARRHENIUS PARAMETERS
  • RING EXPANSION
  • TRIETHYLSILYL RADICALS
  • AMINOACYL RADICALS
  • ORGANIC HALIDES
  • ALKYL RADICALS

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