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

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

doi:10.1021/ja0341743

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 journal › Article › peer-review

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 language	English
Pages (from-to)	5726-5733
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	125
Issue number	19
DOIs	https://doi.org/10.1021/ja0341743
Publication status	Published - 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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@article{c8509b5eb18141e08db436338d08b5fb,

title = "Silylated Cyclohexadienes as New Radical Chain Reducing Reagents: Preparative and Mechanistic Aspects",

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.",

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",

author = "A Studer and S Amrein and F Schleth and T Schulte and Walton, \{John Christopher\}",

year = "2003",

month = may,

day = "14",

doi = "10.1021/ja0341743",

language = "English",

volume = "125",

pages = "5726--5733",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "19",

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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 - https://www.scopus.com/pages/publications/0038296125

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 -

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

Abstract

Keywords

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