1. Addition Reaction of Heteroatom Nucleophiles onto Styrene Catalyzed by Ru(II) Complex
- Author
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Yohei, Oe, Tetsuo, Ohta, and Yoshihiko, Ito
- Subjects
ruthenium catalysis ,atom economy ,ルテニウム触媒 ,求核付加反応 ,オレフィン ,olefins ,アトムエコノミー ,431.35 ,nucleophilic addition reaction - Abstract
二価のルテニウム錯体を用いたヘテロ求核剤のスチレンへの付加反応の開発を達成した.N-メチルトシルアミドとスチレンの反応を, [(p-cymene)RuCl2]2,AgOTf とDppBzを混ぜて発生させた触媒(1 mol% Ru)存在下,クロロホルム中,18時間加熱還流したところ,N-メチル-N-(1-フェニルエチル)トシルアミドが収率83%で得られた.NMR実験,FAB-MSスペクトルおよびX線結晶構造解析によって,[(p-cymene)RuOTf(DppBz)]OTfがクロロホルム中加熱還流下で[(p-cymene)RuCl2]2,AgOTf,1,2-bis(diphenylphosphino)benzene (DppBz)を反応させることによって生成していることが明らかになった.単離した[(p-cymene)RuOTf(DppBz)]OTfは,N-メチルトシルアミド,4-エチル安息香酸および2-フェニルエタノールのクロロホルム中でのスチレンへの付加反応に良好な触媒活性を示し,対応する付加生成物が好収率で得られた., Development of a novel Ru(II) complex-catalyzed addition reaction of heteroatom nucleophiles onto styrene was achieved. Thus, the reaction of N-methyltosylamide with styrene was carried out in the presence of 1 mol% Ru of catalysis generated by mixing [(p-cymene)RuCl2]2, AgOTf and DppBz in CHCl3 at reflux for 18 h to give N-methyl-N-(1-phenylethyl)tosylamide in 83% yield. NMR experiments, FAB-MS spectrum and X-ray analysis revealed that [(p-cymene)RuOTf(DppBz)]OTf was generated in situ by mixing [(p-cymene)RuCl2]2, AgOTf and 1,2-bis(diphenylphosphino)benzene (DppBz) in refluxed CHCl3. Isolated [(p-cymene)RuOTf(DppBz)]OTf showed good catalytic activity for the addition reaction of N-methyltosylamide, 4-ethylbenzoic acid, and 2-phenylethanol onto styrene in CHCl3 to provide the corresponding addition products in good to excellent yields.
- Published
- 2009