Skeletal diversity in Pt- and Au-catalyzed annulations of allenedienes: dissecting unconventional mechanistic pathways,Chemical Science

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Skeletal diversity in Pt- and Au-catalyzed annulations of allenedienes: dissecting unconventional mechanistic pathways
Chemical Science ( IF 7.6 ) Pub Date : 2020-03-27 , DOI: 10.1039/d0sc00650e
Ronald Nelson _{1,

2} , Martín Calvelo ₁ , Rebeca García-Fandiño ₁ , Agustí Lledós ₃ , Gregori Ujaque ₃ , José L Mascareñas ₁ , Fernando López _{1,

4}

Affiliation

We describe the discovery of unprecedented annulation processes of 1,7-allenedienes, promoted by Pt or Au catalysts. These transformations revealed mechanistic pathways that had not been previously observed in reactions involving carbophilic catalysis. In particular, we have found that allenedienes bearing a silyl ether in the carbon tether connecting the diene and the allene divergently afford cyclopropane-embedded tricyclic derivatives, 6,6-fused bicarbocyclic products or 5,6-fused bicarbocyclic systems, depending on the type of Au or Pt catalyst used. We have carried out experimental and computational studies that shed light on the mechanistic reasons behind this rich and unusual skeletal divergence, and provide new lessons on the drastic influence of platinum ancillary ligands on the reaction outcome.

中文翻译：

Pt 和 Au 催化的联二烯成环的骨骼多样性：剖析非常规机制途径

我们描述了由 Pt 或 Au 催化剂促进的 1,7-联二烯的前所未有的环化过程的发现。这些转变揭示了以前在涉及亲碳催化的反应中未观察到的机制途径。特别是，我们发现在连接二烯和丙二烯的碳链中带有甲硅烷基醚的丙二烯不同地提供环丙烷嵌入的三环衍生物、6,6-稠合双碳环产物或5,6-稠合双碳环体系，具体取决于类型使用Au或Pt催化剂。我们进行了实验和计算研究，揭示了这种丰富且不寻常的骨骼分歧背后的机制原因，并为铂辅助配体对反应结果的巨大影响提供了新的教训。

更新日期：2020-03-27

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