钯催化苯乙烯类分子胺氟化反应研究

doi:10.6023/A12100835

化学学报 ›› 2012, Vol. 70 ›› Issue (23): 2404-2407.DOI: 10.6023/A12100835 上一篇下一篇

研究通讯

钯催化苯乙烯类分子胺氟化反应研究

朱海涛, 刘国生

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 E-mail:gliu@mail.sioc.ac.cn
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

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).

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1. 钯催化苯乙烯类分子胺氟化反应研究.PDF(493KB)

摘要/Abstract

报道了烯烃分子间的氧化双官能团化反应, 用金属钯作为金属催化剂, 三价碘为氧化剂, 氟化银为氟源, 磺酰胺类为亲核试剂, 实现了苯乙烯的分子间胺氟化反应, 得到α-F代苯乙胺类化合物; 反应是经过烯烃的反马氏氮钯化得到碳钯键, 再经过三价碘氧化成高价钯的中间体来形成C—F键, 在分子中的特定位置引入氟原子. 该反应的一个特点是选择性地得到反马氏胺氟产物.

关键词: 钯, 胺氟化, 反马氏胺钯化, 苯乙烯, 烯烃双官能团化

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

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朱海涛, 刘国生. 钯催化苯乙烯类分子胺氟化反应研究[J]. 化学学报, 2012, 70(23): 2404-2407.

Zhu Haitao, Liu Guosheng. Palladium-Catalyzed Oxidative Aminofluorination of Styrenes[J]. Acta Chimica Sinica, 2012, 70(23): 2404-2407.

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参考文献

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钯催化苯乙烯类分子胺氟化反应研究

Palladium-Catalyzed Oxidative Aminofluorination of Styrenes

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