Citation: Yu Jiao, Lin Jinhong, Xiao Jichang. ZnO-Promoted Wittig gem-Difluoroolefination of Aldehydes with [Ph₃P⁺CF₂H·Br^-][J]. Chinese Journal of Organic Chemistry, ;2019, 39(1): 265-269. doi: 10.6023/cjoc201806024 shu

ZnO-Promoted Wittig gem-Difluoroolefination of Aldehydes with [Ph₃P⁺CF₂H·Br^-]

Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Xiao Jichang, jchxiao@sioc.ac.cn
Received Date: 15 June 2018
Revised Date: 6 July 2018
Available Online: 24 January 2018
Fund Project: the Chinese Academy of Sciences XDA02020106the Key Research Program of Frontier Sciences (CAS) QYZDJSSW-SLH049the National Natural Science Foundation of China 21672242the National Basic Research Program of China 973计划Project supported by the National Basic Research Program of China (973 Program, No. 2015CB931903), the National Natural Science Foundation of China (Nos. 21421002, 21472222, 21502214, 21672242), the Chinese Academy of Sciences (Nos. XDA02020105, XDA02020106), and the Key Research Program of Frontier Sciences (CAS) (No. QYZDJSSW-SLH049)the National Natural Science Foundation of China 21502214the National Natural Science Foundation of China 21421002the National Basic Research Program of China 2015CB931903the National Natural Science Foundation of China 21472222the Chinese Academy of Sciences XDA02020105

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Wittig gem-difluoroolefination of aldehydes with difluoromethyl phosphonium salt (Ph₃P⁺CF₂H·Br^-) by using zinc oxide as a base is described. Although the proton in the CF₂H group is acidic and a base could easily lead to its deprotonation to form ylide (Ph₃P⁺CF₂^-), the attack of the base at the positive phosphorus atom may also take place to produce a nucleophilic [HCF₂^-] equivalent, and then nucleophilic difluoromethylation instead of Wittig reaction would occur. The use of ZnO as the base favored the Wittig reaction and the nucleophilic difluoromethylation was not observed. Furthermore, the excessive ZnO and Zn^Ⅱ salts produced from ZnO could be easily removed by filtration, which may be convenient for the purification process.
- Wittig,
- gem-difluoroolefination,
- aldehydes,
- difluoromethyl phosphonium salt,
- zinc oxide
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沈阳化工大学材料科学与工程学院沈阳 110142

ZnO-Promoted Wittig gem-Difluoroolefination of Aldehydes with [Ph3P+CF2H·Br-]

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通讯作者: 陈斌, bchen63@163.com

ZnO-Promoted Wittig gem-Difluoroolefination of Aldehydes with [Ph₃P⁺CF₂H·Br^-]