Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (10): 3390-3397.DOI: 10.6023/cjoc202206053 Previous Articles     Next Articles

Special Issue: 不对称催化专辑


双铑(II)/Xantphos催化的C—H官能团化/烯丙基烷基化串联: 从N-芳基-α-重氮-β-酮酯简便制备3-酰基-3-烯丙基氧化吲哚衍生物

李芳洁a,b, 卢斌b, 刘阳a,*(), 王晓明b,c,*()   

  1. a 肿瘤微环境响应药物研究湖南省重点实验室 湖南省分子靶标新药研究 南华大学 衡阳医学院药学院协同创新中心 湖南衡阳 421001
    b 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 分子合成科学卓越创新中心 上海 200032
    c 中国科学院大学杭州高等研究院 化学与材料科学学院 杭州 310024
  • 收稿日期:2022-06-28 修回日期:2022-08-26 发布日期:2022-11-02
  • 通讯作者: 刘阳, 王晓明
  • 基金资助:

Dirhodium/Xantphos-Catalyzed Tandem C—H Functionalization/Allylic Alkylation: Direct Access to 3-Acyl-3-allyl Oxindole Derivatives from N-Aryl-α-diazo-β-keto Amides

Fangjie Lia,b, Bin Lub, Yang Liua(), Xiaoming Wangb,c()   

  1. a Hunan Provincial Key Laboratory of Tumor Microenvironment Responsive Drug Research, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, School of Pharmacology, Hengyang Medical School, University of South China, Hengyang, Hunan 421001
    b State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
    c School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024
  • Received:2022-06-28 Revised:2022-08-26 Published:2022-11-02
  • Contact: Yang Liu, Xiaoming Wang
  • Supported by:
    National Natural Science Foundation of China(21821002)

A novel [Rh2]/Xantphos-catalyzed one-pot sequence for the synthesis of diverse 3-acyl-3-allyl oxindole derivatives from easily available N-aryl-α-diazo-β-keto amides and allylic compounds has been developed. The notable features of this work include ease of operation, mild reaction conditions, good functional group compatibility and facile diversification of the products. Preliminary mechanistic studies indicate a tandem carbene-induced C—H functionalization and Rh(II)/Xantphos catalyzed allylic alkylation process. Moreover, the choice of Xantphos as the ligand is critical to enable the allylic alkylation process in this catalysis.

Key words: dirhodium(II), diazo compounds, oxindoles, quaternary centers, relay catalysis