Yoshida Yuto, Okada Waka, Takada Kazutake, Nakamura Shuichi, Yasukawa Naoki
Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
Org Lett. 2025 Mar 21;27(11):2542-2547. doi: 10.1021/acs.orglett.4c04701. Epub 2025 Jan 10.
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.
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。
