Direct Experimental Characterization of the Ferrier Glycosyl Cation in the Gas Phase,Organic Letters

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Direct Experimental Characterization of the Ferrier Glycosyl Cation in the Gas Phase
Organic Letters ( IF 4.9 ) Pub Date : 2020-11-05 , DOI: 10.1021/acs.orglett.0c03301
Kim Greis _{1,

2} , Carla Kirschbaum _{1,

2} , Sabrina Leichnitz _{1,

3} , Sandy Gewinner ₂ , Wieland Schöllkopf ₂ , Gert von Helden ₂ , Gerard Meijer ₂ , Peter H. Seeberger _{1,

3} , Kevin Pagel _{1,

2}

Affiliation

The Ferrier rearrangement reaction is crucial for the synthesis of pharmaceuticals. Although its mechanism was described more than 50 years ago, the structure of the intermediate remains elusive. Two structures have been proposed for this Ferrier glycosyl cation: a 1,2-unsaturated cation that is resonance-stabilized within the pyranose ring or a cation that is stabilized by the anchimeric assistance of a neighboring acetyl group. Using a combination of gas-phase cryogenic infrared spectroscopy in helium nanodroplets and first-principles density functional theory, we provide the first direct structural characterization of Ferrier cations. The data show that both acetylated glucal and galactal lead to glycosyl cations of the dioxolenium type.

中文翻译：

气相中氨基糖基阳离子的直接实验表征

Ferrier重排反应对于药物合成至关重要。尽管其机理已有50多年的历史，但中间体的结构仍然难以捉摸。对于该费勒糖基阳离子已经提出了两种结构：在吡喃糖环内共振稳定的1，2-不饱和阳离子或通过相邻乙酰基的嵌合辅助而稳定的阳离子。结合氦纳米液滴中的气相低温红外光谱技术和第一性原理密度泛函理论，我们提供了Ferrier阳离子的第一个直接结构表征。数据表明乙酰化的葡糖基和半乳糖基均导致二氧戊环类型的糖基阳离子。

更新日期：2020-11-21

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