Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (23): 2404-2407.DOI: 10.6023/A12100835 Previous Articles     Next Articles



朱海涛, 刘国生   

  1. 金属有机化学国家重点实验室 中国科学院上海有机化学研究所 上海 200032
  • 投稿日期:2012-10-29 发布日期:2012-11-12
  • 通讯作者: 刘国生
  • 基金资助:
    项目受科技部973 (No. 2009CB825300);国家自然科学基金(Nos. 0972175, 20923005)和上海市科委(No. 11JC1415000)资助.

Palladium-Catalyzed Oxidative Aminofluorination of Styrenes

Zhu Haitao, Liu Guosheng   

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2012-10-29 Published:2012-11-12
  • Supported by:
    Project supported by the 973 Program of China (No. 2009CB825300), the National Natural Science Foundation of China (Nos. 20972175, 20923005), and the Science and Technology Commission of the Shanghai Municipality (No. 11JC1415000).

A novel palladium-catalyzed intermolecular aminofluorination of styrenes has been developed, using silver fluoride as the fluorine source, palladium diacetate as metal catalyst, and acetonitrile as solvent at room temperature. As regard to the mechanism, we proposed that the anti-Markovnikov aminopalladation was involved in the construction of C—N bond. This selectivity of nucleophilic palladation of styrenes is different from that reported before. In order to verify our proposed mechanism, we conducted the competition experiments using styrenes containing different functional groups. The results are consistent with our analysis. We belive that the C—F bond is formed after the Pd(II)-C is oxidized to Pd(IV)-C. Namely, the high oxidative state palladium is involved in catalytic cycle. In all, this transformation represents a novel strategy to synthesize a variety of vicinal fluoroamine derivatives.

Key words: palladium, aminofluorination, anti-Markovnikov, styrene