自旋标记的α-/β-半乳糖神经酰胺和葡萄糖神经酰胺作为电子顺磁共振探针的合成
Synthesis of Spin-Labeled α-/β-Galactosylceramides and Glucosylceramides as Electron Paramagnetic Probes.
作者信息
Rohokale Rajendra, Mane Rajendra, Malet Lucie, Dessain Selena, Guo Zhongwu
机构信息
Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
UF Health Cancer Center, University of Florida, Gainesville, Florida 32611, United States.
出版信息
J Org Chem. 2025 Jan 10;90(1):877-888. doi: 10.1021/acs.joc.4c02423. Epub 2024 Dec 16.
Abstract
α-/β-Galactosylceramide (GalCer) and glucosylceramide (GlcCer) derivatives having a radical label at the 6--position suitable for electron paramagnetic resonance spectroscopic studies were synthesized by a diversity-oriented strategy that is highlighted by the efficient glycosylation of a lipid precursor and late-stage ceramide assembly to enable lipid diversification. The strategy was also utilized to synthesize natural α-/β-GalCers and GlcCers. Furthermore, the involved azido-intermediates are flexible platforms to access various other GalCer and GlcCer derivatives.
摘要
通过一种以多样性为导向的策略合成了在6-位具有适合电子顺磁共振光谱研究的自由基标记的α-/β-半乳糖神经酰胺（GalCer）和葡萄糖神经酰胺（GlcCer）衍生物，该策略的突出特点是脂质前体的高效糖基化和后期神经酰胺组装以实现脂质多样化。该策略还用于合成天然α-/β-GalCers和GlcCers。此外，所涉及的叠氮中间体是获得各种其他GalCer和GlcCer衍生物的灵活平台。
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2
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