Acta Chim. Sinica ›› 2018, Vol. 76 ›› Issue (5): 377-381.DOI: 10.6023/A18020073 Previous Articles     Next Articles



王明a, 姜雪峰a,b   

  1. a 华东师范大学化学与分子工程学院 上海 200062;
    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 上海 200032
  • 投稿日期:2018-02-20 发布日期:2018-03-13
  • 通讯作者: 姜雪峰,;Tel.:+86-021-52133654
  • 基金资助:


Efficient Fluoren-9-ones Construction through CO/I Exchange of Diaryliodonium Salts

Wang Minga, Jiang Xuefenga,b   

  1. a School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2018-02-20 Published:2018-03-13
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21722202, 21672069, 21472050, 21502054), Doctoral Fund of Ministry of Education of China (No. 20130076110023).

Fluoren-9-ones derivatives have attracted much attention due to their extensively applications in pharmaceuticals, natural products and photoelectric materials. In recent decades, C—H bond functionalization is the most powerful method to access fluorenone skeleton. Although these interesting studies exploited highly efficient routes to the fluoren-9-one, in many examples, it is easy to produce two isomers in the meta-substituted substrates because of the existence of two different C—H bonds in the ortho-position. It is still indispensable to develop efficient methods for fluoren-9-ones construction. Diaryliodonium salt as a stable and easily prepared reagent reported by Hartmann and Meyer since 1894, which has been one of the most efficient arylation reagents in organic synthesis. Generally, diaryliodonium salt was employed as a single arylation reagent. In the past few years, the both aryl employments of diaryliodonium salt were explored due to the improvement of atom economy. Recently, we developed the atom exchange reactions of intramolecular and intermolecular diaryliodonium salts for sulfide, selenide, sulfone, acridine and carbazole constructions, which could employ both aryl groups of diaryliodonium salt. Continuous with our research of using such atom exchange method for significant molecular construction, herein, a CO/I exchange method of diaryliodonium salts with carbon monoxide was developed for construction of functional fluoren-9-ones. Both aryl groups in diaryliodonium salt were fully exerted in this transformation, which proceeded smoothly in a CO balloon atmosphere to afford the desired products in moderate to excellent yields with good functional-group compatibility. Note that this protocol avoided the emerging of isomers, which were easy to be formed in C—H bond functionalization method. A representative procedure for this reaction is as following:Under a CO atmosphere, Pd(OAc)2 (0.01 mmol), dppf (0.012 mmol), K3PO4 (0.2 mmol), diaryliodonium salts 1 and toluene (1 mL) were added to a flame-dried Schlenk tube. The resulting mixture was stirred at 80℃ for 24 h. Water (5 mL) was added and the solution was extracted with ethyl acetate, organic layers were combined, dried over sodium sulfate. After evaporation of solvent, the residue was purified by column chromatography to give the corresponding products.

Key words: diaryliodonium salt, fluoren-9-one, carbonylation