| dbo:abstract |
The vinylcyclopropane rearrangement or vinylcyclopropane-cyclopentene rearrangement is a ring expansion reaction, converting a vinyl-substituted cyclopropane ring into a cyclopentene ring. Intense experimental as well as computational investigations have revealed that mechanistically, the vinylcyclopropane rearrangement can be thought of as either a diradical-mediated two-step and/or orbital-symmetry-controlled pericyclic process. The amount by which each of the two mechanisms is operative is highly dependent on the substrate. Due to its ability to form cyclopentene rings the vinylcyclopropane rearrangement has served several times as a key reaction in complex natural product synthesis. (en) ビニルシクロプロパン転位（ - てんい、Vinylcyclopropane rearrangement）、あるいはビニルシクロプロパン-シクロペンテン転位（vinylcyclopropane-cyclopentene rearrangement）は、ビニル基を持つシクロプロパン環がシクロペンテン環に変換される、環拡大反応のことである。 数々の実験により、反応機構が解明されてきており、現在はジラジカルを介した二段階反応、または軌道の対称性により起こるペリ環状反応のいずれかにより進行すると考えられている。 シクロペンテン環を構築できるため、天然物の全合成において当反応は利用されている。 (ja) De vinylcyclopropaan-cyclopenteen-omlegging, vaak kortweg VCCO genoemd, is een , waarbij een vinyl-gesubstituteerde cyclopropaanring wordt omgezet in een cyclopenteenring: De reactie werd ontdekt in 1960 tijdens de pyrolyse van , een uitgangsstof voor . Vaak wordt de omlegging beschreven als een sigmatrope omlegging, hoewel de specifieke eigenschappen van de cyclopropaanring de reactie tot een atypisch voorbeeld van de omlegging maken. Ten gevolge van de hoge reactiviteit en het gedeeltelijke π-karakter van de bindingen in de cyclopropaanring, verloopt de reactie vaak al bij relatief lage temperaturen. Behalve thermisch kan de reactie ook als fotochemische reactie worden uitgevoerd. Naast de sigmatrope reactieroute behoort ook de reactie via een diradicaal tot de mogelijkheden: In een analoge reactie wordt een omgezet in het analoge cyclohexeen. Een microgolfoven treedt daarbij op als de energiebron voor de reactie. (nl) 乙烯基环丙烷重排（英文：vinylcyclopropane rearrangement，或称乙烯基环丙烷-环戊烯重排）是将乙烯基取代的环丙烷变为环戊烯的扩环反应。 实验性与计算性研究表明，乙烯基环丙烷重排反应的机理被认为是双自由基介导的两步过程和/或轨道对称性控制的周环过程，两种机理在具体反应中起的作用主要取决于底物。 由于能用于构建环戊烯环，乙烯基环丙烷重排反应已被用于合成复杂天然产物中的关键步骤。 (zh) |
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| rdfs:comment |
ビニルシクロプロパン転位（ - てんい、Vinylcyclopropane rearrangement）、あるいはビニルシクロプロパン-シクロペンテン転位（vinylcyclopropane-cyclopentene rearrangement）は、ビニル基を持つシクロプロパン環がシクロペンテン環に変換される、環拡大反応のことである。 数々の実験により、反応機構が解明されてきており、現在はジラジカルを介した二段階反応、または軌道の対称性により起こるペリ環状反応のいずれかにより進行すると考えられている。 シクロペンテン環を構築できるため、天然物の全合成において当反応は利用されている。 (ja) 乙烯基环丙烷重排（英文：vinylcyclopropane rearrangement，或称乙烯基环丙烷-环戊烯重排）是将乙烯基取代的环丙烷变为环戊烯的扩环反应。 实验性与计算性研究表明，乙烯基环丙烷重排反应的机理被认为是双自由基介导的两步过程和/或轨道对称性控制的周环过程，两种机理在具体反应中起的作用主要取决于底物。 由于能用于构建环戊烯环，乙烯基环丙烷重排反应已被用于合成复杂天然产物中的关键步骤。 (zh) The vinylcyclopropane rearrangement or vinylcyclopropane-cyclopentene rearrangement is a ring expansion reaction, converting a vinyl-substituted cyclopropane ring into a cyclopentene ring. Intense experimental as well as computational investigations have revealed that mechanistically, the vinylcyclopropane rearrangement can be thought of as either a diradical-mediated two-step and/or orbital-symmetry-controlled pericyclic process. The amount by which each of the two mechanisms is operative is highly dependent on the substrate. (en) De vinylcyclopropaan-cyclopenteen-omlegging, vaak kortweg VCCO genoemd, is een , waarbij een vinyl-gesubstituteerde cyclopropaanring wordt omgezet in een cyclopenteenring: De reactie werd ontdekt in 1960 tijdens de pyrolyse van , een uitgangsstof voor . Naast de sigmatrope reactieroute behoort ook de reactie via een diradicaal tot de mogelijkheden: In een analoge reactie wordt een omgezet in het analoge cyclohexeen. Een microgolfoven treedt daarbij op als de energiebron voor de reactie. (nl) |
| rdfs:label |
ビニルシクロプロパン転位 (ja) Vinylcyclopropaan-cyclopenteen-omlegging (nl) Vinylcyclopropane rearrangement (en) 乙烯基环丙烷重排反应 (zh) |
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