美国加州大学Garg, Neil K.团队报道了1,2,3-环己三烯及其衍生物的应变促进反应。相关研究成果于2023年4月19日发表在《自然》。

自1825年以来，对分子式为C6H6的化合物（尤其是苯）研究一直是严格科学研究的主题。在这些化合物中，1,2,3-环己三烯在很大程度上被忽视了。与苯相比，这种应变异构体的能量要高得多（约100 kcal/mol），并且与它的近亲苯并炔和1,2-环己二烯一样，应该经历应变促进的反应。然而，对1，2，3-环己三烯的实验研究很少。

该文中，研究人员证明了1，2，3-环己三烯及其衍生物参与多种反应模式，包括不同的环加成、亲核加成和σ-键插入。1，2，3-环己三烯不对称衍生物的实验和计算研究表明，尽管应变三烯具有高反应性和短寿命，但它们仍有可能进行高选择性反应。最后，将1，2，3-环己三烯整合到多步合成序列中，证明了它们在快速组装拓扑和立体化学复杂分子方面的实用性。总之，这些努力将推动对应变C6H6异构体1,2,3-环己三烯及其衍生物的进一步研究，以及它们在重要化合物合成中的战略应用。

附：英文原文

Title: Strain-promoted reactions of 1,2,3-cyclohexatriene and its derivatives

Author: Kelleghan, Andrew V., Bulger, Ana S., Witkowski, Dominick C., Garg, Neil K.

Issue&Volume: 2023-04-19

Abstract: Since 18251, studies of compounds with the molecular formula C6H6 – most notably benzene – have been the subject of rigorous scientific investigation2,3,4,5,6,7. Of these compounds, 1,2,3-cyclohexatriene has been largely overlooked. This strained isomer is substantially (~100 kcal/mol) higher in energy compared to benzene and, like its relatives benzyne and 1,2-cyclohexadiene, should undergo strain-promoted reactions. However, few experimental studies of 1,2,3-cyclohexatriene are known8,9,10,11,12. We demonstrate that 1,2,3-cyclohexatriene and its derivatives participate in a host of reaction modes including diverse cycloadditions, nucleophilic additions, and σ-bond insertions. Experimental and computational studies of an unsymmetrical derivative of 1,2,3-cyclohexatriene demonstrate the potential for highly selective reactions of strained trienes despite their high reactivity and short lifetimes. Finally, integration of 1,2,3-cyclohexatrienes into multistep synthetic sequences demonstrates their utility in rapidly assembling topologically and stereochemically complex molecules. Collectively, these efforts should fuel the further investigation of the strained C6H6 isomer 1,2,3-cyclohexatriene and its derivatives, as well as their strategic application in the synthesis of important compounds.

DOI: 10.1038/s41586-023-06075-8

Source: https://www.nature.com/articles/s41586-023-06075-8