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gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction
Alternative Title以二氟甲基(2-吡啶基)砜试剂对双芳基酮和可烯醇化醛的偕二氟烯基化: 对Julia-Kocienski成烯化反应的新理解
Gao B(高兵); Zhao YC(赵延川); Hu MY(胡明友); Ni CF(倪传法); Hu JB(胡金波)
2014
Source PublicationChem.-Eur. J.
Volume20Issue:25Pages:7803-7810
AbstractThe direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rearrangement of the carbinol intermediate; the gem-difluoroolefination is otherwise difficult to achieve through a conventional Julia-Kocienski olefination protocol under basic conditions due to the retro-aldol type decomposition of the key intermediate. Efficient gem-difluoroolefination of aliphatic aldehydes was achieved by the use of an amide base generated in situ (from CsF and tris(trimethylsilyl)amine), which diminishes the undesired enolization of aliphatic aldehydes and provides a powerful synthetic method for chemoselective gem-difluoroolefination of multi-carbonyl compounds. Our results provide new insights into the mechanistic understanding of the classical Julia-Kocienski reaction.
Subject Area氟化学
DOI10.1002/chem.201402183
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Indexed BySCI
Language英语
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Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/38821
Collection中科院有机氟化学重点实验室
Corresponding AuthorHu JB(胡金波)
Affiliation中科院上海有机化学研究所
Recommended Citation
GB/T 7714
Gao B,Zhao YC,Hu MY,et al. gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction[J]. Chem.-Eur. J.,2014,20(25):7803-7810.
APA 高兵,赵延川,胡明友,倪传法,&胡金波.(2014).gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction.Chem.-Eur. J.,20(25),7803-7810.
MLA 高兵,et al."gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction".Chem.-Eur. J. 20.25(2014):7803-7810.
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