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Representative Reaction Conditions. Into a two-neck 50 mL flask, charged with dioxygen, was added a mixture of alkene (2 mmol) and cobalt-(II) complex (0.10 mmol) in 1,2-dichloroethane (DCE) (5 mL). Then, triethylsilane (4 mmol) was added via a 1.0 mL gaslight syringe, and the reaction mixture was stirred vigorously under an oxygen atmosphere at room temperature.
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0042771134
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In all cases, the resulting triethylsilyl peroxide could not be separated from the remaining alkene. Therefore, after treatment of this mixture with one portion of concentrated HCl in MeOH, the peroxide was isolated in the form of the corresponding hydroperoxide.
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Conversion in the complex 4-catalyzed peroxidation was much lower than that in the conventional Co(II)-catalyzed reaction, which would be due to the stabilization of complex 4 by the coordinated pyridine as a sixth ligand.
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31
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2 In the present reaction, however, no product derived from such an insertion reaction was observed.
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3SiOOH at the first step and the following addition to the alkene is not important in the Isayama-Mukaiyama reaction.
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