We report the synthesis of functionalized cycloheptanes by thermal electrocyclization of heptatrienyl anions under mild conditions. In addition, we disclose the first examples of this electrocyclization manifold conducted under catalytic conditions. Previously, electrocyclization of heptatrienyl systems required formation of anions with a strong base, resulting in limited functional group compatibility. We demonstrate that polarization of heptatrienyl anions using strategically positioned electron-withdrawing groups lowers the energy landscape of the reaction by stabilizing both the acyclic heptatrienyl anion and cycloheptadienyl product. Divergent reactivity is observed between aliphatic and aromatic substrates, with the latter requiring only catalytic amounts of base for complete conversion. This can be rationalized by the relative stability of the acyclic and cyclic anions and their ability to participate in a chain reaction process.

中文翻译：

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庚三烯基阴离子的温和催化电环化

我们报道了在温和条件下通过庚三烯基阴离子的热电环化合成官能化环庚烷。此外，我们公开了在催化条件下进行的这种电环化歧管的第一个例子。此前，庚三烯基体系的电环化需要形成具有强碱的阴离子，导致官能团相容性有限。我们证明，使用策略性定位的吸电子基团对庚三烯基阴离子进行极化，可以稳定无环庚三烯基阴离子和环庚二烯基产物，从而降低反应的能量图。在脂肪族和芳香族底物之间观察到不同的反应性，后者仅需要催化量的碱即可完全转化。这可以通过无环和环状阴离子的相对稳定性以及它们参与链式反应过程的能力来合理化。