伪-Crotyl-伪-difluoroboranyloxy-amides: Structure and Reactivity of Isolable Intermediates in Stereospecific 伪-Ketol Rearrangements
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- 作者：Jan Ro脽bach ; Klaus Harms ; Ulrich Koert
- 刊名：Organic Letters
- 出版年：2015
- 出版时间：June 19, 2015
- 年：2015
- 卷：17
- 期：12
- 页码：3122-3125
- 全文大小：367K
- ISSN：1523-7052
文摘
The stereospecific BF3-mediated 伪-ketol rearrangement of 尾-hydroxy-伪-ketoamides yields isolable 2-difluoroboranyloxy-3-keto-amides. X-ray and NMR analysis reveal a carbonyl coordination of the boron by the amide not the ketone. The boron complexes are air-stable solids, can be purified by silica gel chromatography, and exhibit novel reactivity in bromination and superior stereoselectivity in dipolar cycloaddition reactions.