The aromatic ene reaction.
The aromatic ene reaction.
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烯反应是一个周环过程，其中具有烯丙基氢原子（烯供体）的烯烃与第二不饱和物质（亲烯体）反应形成具有转位π键的新产物。其中烯烃组分嵌入芳环中的芳烯反应仅在少数（四）个实例中被报道，并且以低收率（≤6％）进行。在这里，我们展示了有效的芳香烯反应，其中热生成的芳炔与侧烷基芳烃取代基结合生成脱芳构异甲苯，其本身是另一种多用途但罕见的反应中间体。我们的实验以计算研究为指导，揭示了有利于芳香烯过程的结构特征。我们继续确定了包含三个反应的级联：（i）十六氢-狄尔斯-阿尔德（用于芳基生成），（ii）分子内芳香烯和（iii）双分子阿尔德烯。从最终产品的结构复杂性、相当大的范围以及这些多阶段、无试剂和副产物的单锅转化的整体效率来看，这种级联的力量是显而易见的。
The ene reaction is a pericyclic process in which an alkene having an allylic hydrogen atom (the ene donor) reacts with a second unsaturated species (the enophile) to form a new product with a transposed π-bond. The aromatic ene reaction, in which the alkene component is embedded in an aromatic ring, has only been reported in a few (four) instances and has proceeded in low yield (≤6%). Here we show efficient aromatic ene reactions in which a thermally generated aryne engages a pendant m-alkylarene substituent to produce a dearomatized isotoluene, itself another versatile but rare reactive intermediate. Our experiments were guided by computational studies that revealed structural features conducive to the aromatic ene process. We proceeded to identify a cascade comprising three reactions: (i) hexadehydro-Diels-Alder (for aryne generation), (ii) intramolecular aromatic ene, and (iii) bimolecular Alder ene. The power of this cascade is evident from the structural complexity of the final products, the considerable scope, and the overall efficiency of these multi-stage, reagent- and byproduct-free, single-pot transformations.
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