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| In an attempt to rationalize all these results, the following mechanism can be proposed (Scheme 3). The catalytic cycle might be initiated by a nucleophilic addition of triphenylphosphine to the electron-deficient allene 2. The enolate 6 then deprotonates the azole 1 generating the nucleophilic species 5 and the vinylphosphonium 4. Consecutively, nucleophilic addition of 5 to vinylphosphonium 4 leads to the ylide 7. Finally, enolate 8 is obtained by prototropy and then undergoes a b-elimination affording the final g-addition allylazole 3 and regenerating the nucleophilic catalyst. |
| 嘗試為這些結(jié)果找合理的理由,推測的機(jī)理如下(方案3)。催化循環(huán)過程可能是由三苯基磷引發(fā),親核加成到缺電子的丙二烯2上。烯醇6脫去唑1的質(zhì)子生成親核基團(tuán)5 和乙烯基磷4.接著,5親核加成至乙烯基磷生成內(nèi)鎓鹽7.最后,由質(zhì)子轉(zhuǎn)移獲得烯醇化合物8,烯醇化合物8經(jīng)歷β-消除反應(yīng),反應(yīng)提供了最終的g加成的丙烯唑3和再生了親核催化劑。 |

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