gem-Difluoroolefination of Diaryl Ketones and Enolizable Aldehydes with Difluoromethyl 2-Pyridyl Sulfone: New Insights into the Julia-Kocienski Reaction
文献类型：期刊论文
| 作者 | 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.
 |
| 出版日期 | 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 |
| 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. |
入库方式： OAI收割
来源：上海有机化学研究所
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