Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized.,Angewandte Chemie International Edition

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Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-06-08 , DOI: 10.1002/anie.202006992
Pengjin Qin ₁ , Li-An Wang ₁ , Joseph M O'Connor ₁ , Kim K Baldridge ₂ , Yifan Li ₁ , Burak Tufekci ₁ , Jiyue Chen ₁ , Arnold L Rheingold ₁

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Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition‐metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.

中文翻译：

Triene6π电环化的过渡金属催化：实现的π络合策略。

三烯6π电环化是一种具有重大历史和现实意义的反应，其中共轭三烯经历了一致的立体有择的环异构化为环己二烯。为了规避通常苛刻的反应条件带来的限制，化学家们长期以来一直在寻求基于金属-烯烃配位的活化能来开发催化变体的方法。在这里，我们演示了通过利用[（C ₅ H ₅）Ru（NCMe）₃ ] PF ₆首次成功实施该策略用作抗热环化的高度取代的三烯的可旋转6π电环化的前催化剂。力学和计算研究表明，六向过渡金属配位可降低闭环的能量屏障。这项工作为开发新的立体选择性电环化催化剂奠定了基础。

更新日期：2020-06-08

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