TY - JOUR
T1 - Silylated Cyclohexadienes as New Radical Chain Reducing Reagents: Preparative and Mechanistic Aspects
AU - Studer, A
AU - Amrein, S
AU - Schleth, F
AU - Schulte, T
AU - Walton, John Christopher
PY - 2003/5/14
Y1 - 2003/5/14
N2 - 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.
AB - 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.
KW - NORMAL-BUTYLTIN HYDRIDE
KW - ELECTRON-SPIN-RESONANCE
KW - ABSOLUTE RATE CONSTANTS
KW - BETA-KETO-ESTERS
KW - ARRHENIUS PARAMETERS
KW - RING EXPANSION
KW - TRIETHYLSILYL RADICALS
KW - AMINOACYL RADICALS
KW - ORGANIC HALIDES
KW - ALKYL RADICALS
UR - http://www.scopus.com/inward/record.url?scp=0038296125&partnerID=8YFLogxK
UR - http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/2003/125/i19/abs/ja0341743.html
U2 - 10.1021/ja0341743
DO - 10.1021/ja0341743
M3 - Article
SN - 0002-7863
VL - 125
SP - 5726
EP - 5733
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -