Yan Si-Shun, Zhu Lei, Ye Jian-Heng, Zhang Zhen, Huang He, Zeng Huiying, Li Chao-Jun, Lan Yu, Yu Da-Gang
Key Laboratory of Green Chemistry & Technology of Ministry of Education , College of Chemistry , Sichuan University , 29 Wangjiang Road , Chengdu 610064 , P. R. China . Email:
School of Chemistry and Chemical Engineering , Chongqing University , Chongqing 400030 , P. R. China . Email:
Chem Sci. 2018 Apr 30;9(21):4873-4878. doi: 10.1039/c8sc01299g. eCollection 2018 Jun 7.
The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO to generate important aryl acetic acids is reported. Besides aldehyde hydrazones, a variety of ketone hydrazones, which have not been successfully applied in previous umpolung reactions with other reactive electrophiles, also show high reactivity and selectivity under mild conditions. Moreover, this operationally simple protocol features good functional group tolerance, is readily scalable, and offers easy derivation of important structures, including bioactive felbinac and adiphenine. Computational studies reveal that this umpolung reaction proceeds through the generation of a Ru-nitrenoid followed by concerted [4 + 2] cycloaddition with CO.
报道了首例钌催化腙与一氧化碳发生极性反转羧基化反应生成重要的芳基乙酸。除了醛腙之外，各种酮腙在之前与其他活性亲电试剂的极性反转反应中未成功应用，但在温和条件下也表现出高反应活性和选择性。此外，该操作简单的方法具有良好的官能团耐受性，易于放大规模，并能方便地衍生出重要结构，包括具有生物活性的非诺洛芬和阿地芬宁。计算研究表明，这种极性反转反应是通过生成一个钌氮宾中间体，然后与一氧化碳进行协同的[4 + 2]环加成反应来进行的。
