2026-03-18 東京科学大学
![ニトロアレーンとグリニャール反応剤から 多官能ビアリールを⼀段階合成 −ベンジジン型[5,5]-転位を制御する新合成戦略−](https://www.isct.ac.jp/cms/contents/data/1/3510/component/file/251830c90f402bc613a3a09ba890d5e1.webp "ニトロアレーンとグリニャール反応剤から 多官能ビアリールを⼀段階合成 −ベンジジン型[5,5]-転位を制御する新合成戦略−")
図1. ニトロアレーンとアリールグリニャール反応剤から多官能ビアリールおよびベンゾイミダゾールの一段階で構築するベンジジン型[5,5]-転位反応の概略
＜関連情報＞
- https://www.isct.ac.jp/ja/news/2p9z912c2x3k
- https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202503607
マグネシウム促進ベンジジン型転位反応による多官能性ビアリールの位置選択的合成 Magnesium-Promoted Benzidine-Type Rearrangement for Regioselective Construction of Polyfunctionalized Biaryls
Shumpei Saito, Manato Ishida, Yuki Busujima, Miki Ebihara, Kodai Kohama, Naomi Tanaka, Eitaro Toya, Minami Nakamura, Takashi Kanamori, Tadaomi Furuta, Shota Matsumoto …
Chemistry – A European Journal Published: 15 February 2026
DOI:https://doi.org/10.1002/chem.202503607
ABSTRACT
A magnesium-promoted benzidine-type rearrangement of 1,3-dihalonitroarenes with aryl Grignard reagents has been developed, enabling the highly regioselective and efficient synthesis of 1-amino-1’-hydroxy-4,4’-biaryls under simple, transition-metal-free conditions. A rational substrate design—featuring an ortho substituent (R) and two meta-substituted electron-withdrawing groups (X, Y)—steers the reaction trajectory, converting a previously minor [5,5]-sigmatropic migration into the dominant pathway. The transformation exhibits broad functional-group tolerance, excellent scalability, and provides direct and operationally straightforward access to polyfunctionalized biaryls. Furthermore, trifluoroacetamide-substituted nitroarenes undergo [5,5]-rearrangement followed by intramolecular cyclization to furnish CF3-substituted benzimidazoles with high regioselectivity. Overall, this study expands the conceptual scope of benzidine-type rearrangements and establishes a mechanistically tunable, sustainable strategy for constructing valuable biaryl and heteroaromatic scaffolds.
