Issue 21, 2024

Mild and catalytic electrocyclizations of heptatrienyl anions

Abstract

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.

Graphical abstract: Mild and catalytic electrocyclizations of heptatrienyl anions

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Feb 2024
Accepted
25 Apr 2024
First published
26 Apr 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 8163-8169

Mild and catalytic electrocyclizations of heptatrienyl anions

F. Rasheed, A. Nikolaev, A. Dhesi, T. Zeng, Y. X. Guo, Y. Krishna, S. Komijani and A. Orellana, Chem. Sci., 2024, 15, 8163 DOI: 10.1039/D4SC00926F

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