open access

https://hdl.handle.net/2115/90171

Mechanochemically Generated Calcium-Based Heavy Grignard Reagents and Their Application to Carbon-Carbon Bond-Forming Reactions

英語

Solid-State Reaction

2022-10-10

Wiley-Blackwell

Angewandte chemie-international edition

61(41)

e202207118

In sharp contrast to the use of conventional magnesium-based Grignard reagents (R-MgX), the application of calcium-based heavy Grignard reagents (R-CaX) in organic synthesis remains poorly explored. This is mainly due to the lack of experimentally simple ways to access such organocalcium nucleophiles from readily available starting materials under mild conditions. Here, we show that a mechanochemical technique using ball milling allows the generation of calcium-based heavy Grignard reagents from aryl halides and commercially available calcium metal without complicated pre-activation processes. Notably, all experimental operations can be carried out in air. Our operationally simple protocol enables the rapid development of novel cross-electrophile-coupling reactions mediated by arylcalcium nucleophiles, which are rather difficult using conventional Grignard reagents. This method will allow synthetic chemists to readily access the novel and unique reactivity of organocalcium nucleophiles.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: [FULL CITE], which has been published in final form at https://doi.org/10.1002/anie.202207118. 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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