open access

https://hdl.handle.net/2115/97364

Mechanism-Guided Development of Bifunctional Cyclooctenes as Active, Practical, and Light-Gated Bromination Catalysts

英語

biocompatibility

2024-12-16

Wiley-Blackwell

Chemistry-A European journal

Most molecular catalysts have been developed employing polar functional groups as catalytic sites. However, the use of non-polar functional groups for catalysis has received less attention due to their modest molecular interactions while the bioorthogonal reactivity of non-polar alkenes as substrates is frequently used in click chemistry. In this study, we conducted mechanistic studies on the catalysis of trans-cyclooctene (TCO) derivatives with the strained olefin as the catalytic site using kinetic and computational analyses to aid the design of more active olefin catalysts. The analysis reveals the significant role of the benzyl substituents in accelerating the generation of bromonium species through dispersion interaction in the rate-determining step. Guided by the mechanistic insights, we developed bifunctional TCO catalysts bearing a functionalized benzyl group, taking advantage of the remarkable substituent effects. Experimental studies confirmed the theoretical model and revealed that TCO with a para-hydroxybenzyl group provided excellent catalytic activity. Furthermore, inclusion of the functionalized benzyl groups allowed more readily available and robust cis-cyclooctenes to be used as active catalysts, expanding the practical utility of the olefin catalysts. By using a photochemically labile masking group on the para-hydroxybenzyl substituent, the first light-gated bromination catalyst was developed, enabling spatiotemporal control of the transformation.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Mechanism-Guided Development of Bifunctional Cyclooctenes as Active, Practical, and Light-Gated Bromination Catalysts, which has been published in final form at https://doi.org/10.1002/chem.202404011. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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