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胺连接的硼自由基实现脱氰转化的光催化策略。

Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical.

作者信息

Yoshida Yuto, Okada Waka, Takada Kazutake, Nakamura Shuichi, Yasukawa Naoki

机构信息

Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.

出版信息

Org Lett. 2025 Mar 21;27(11):2542-2547. doi: 10.1021/acs.orglett.4c04701. Epub 2025 Jan 10.

Abstract

Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables the strategic assembly of a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated cyano group transfer (CGT) strategy of malononitriles under photocatalytic conditions. This strategy allows for the cleavage of C(sp)-CN and the formation of C(sp)-D and C(sp) to realize decyanative deuteration and cyclization via radical-polar crossover. Computational studies successfully demonstrated the reactivity of CGT promoters can be accurately assessed.

摘要

通过利用氰基的固有性质在α-官能化后进行脱氰反应,能够实现碳骨架的策略性组装。在此,我们展示了一种在光催化条件下,胺连接的硼自由基介导的丙二腈氰基转移(CGT)策略。该策略允许C(sp)-CN键的断裂以及C(sp)-D和C(sp)键的形成,从而通过自由基-极性交叉实现脱氰氘代和环化反应。计算研究成功证明了CGT促进剂的反应活性可以得到准确评估。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/16f8/11934141/91afa0d3c8d3/ol4c04701_0001.jpg

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