gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction

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	gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction
	Gao B(高兵); Zhao YC(赵延川); Hu MY(胡明友); Ni CF(倪传法); Hu JB(胡金波)
刊名	Chem.-Eur. J.
	2014
卷号	20 期号:25 页码:7803-7810
其他题名	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
通讯作者	胡金波
英文摘要	The 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.
学科主题	氟化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1002/chem.201402183
语种	英语
内容类型	期刊论文
源URL	[http://ir.sioc.ac.cn/handle/331003/38821]
专题	上海有机化学研究所_中科院有机氟化学重点实验室
作者单位	中科院上海有机化学研究所
推荐引用方式 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.