Trifluoromethyl-Radical-Mediated Carbonylation of Alkanes Leading to Ethynyl Ketones
Trifluoromethyl-Radical-Mediated Carbonylation of Alkanes Leading to Ethynyl Ketones
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DOI：
10.1002/hlca.200690228
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发表时间：
2006-10
影响因子：
1.8
通讯作者：
Yoshitaka Uenoyama;T. Fukuyama;K. Morimoto;Osamu Nobuta;Hidefumi Nagai;I. Ryu
中科院分区：
文献类型：
--
作者：
Yoshitaka Uenoyama;T. Fukuyama;K. Morimoto;Osamu Nobuta;Hidefumi Nagai;I. Ryu
以乙炔基三氟甲酮A为单分子链转移试剂，研究了自由基反应条件下烷烃1的羰基化反应。通过该三组分偶联反应制备了良好至中等产率的乙炔基酮2。较高的CO压力以及较低浓度的三氟甲酮A提高了反应效率，而直接加成导致烷基化乙炔3。与与A的反应相反，环己烷（1a）与烯丙基三氟甲酮B（= 2-亚甲基-3-[（三氟甲基）磺酰基]丙酸乙酯）在CO存在下的反应得到羰基化产物的混合物，包括由环己烷、CO和烯丙基三氟甲酮B各自的两个分子形成的8a。
The carbonylation of alkanes 1 under radical-reaction conditions was examined by using ethynyl triflone A as the unimolecular chain-transfer (UMCT) reagent. Good to moderate yields of ethynyl ketones 2 were prepared by means of this three-component coupling reaction. Higher CO pressures as well as lower concentrations of triflone A improved the efficiency of the reaction over the direct addition, the latter leading to alkylated ethynes 3. In contrast to the reaction with A, the reaction of cyclohexane (1a) with allyl triflone B (= ethyl 2-methylene-3-[(trifluoromethyl)sulfonyl]propanoate) in the presence of CO gave a mixture of carbonylation products, including 8a formed from two molecules each of cyclohexane, CO, and allyl triflone B.