武汉大学李阳阳团队报道了从甘氨酸以1,4,2-二恶唑-5-酮糖基立体选择性合成2-脱氧-α-N-糖苷。相关研究成果于2024年5月7日发表在国际顶尖学术期刊《中国化学》。

N-糖苷的合成因其在碳水化合物化学中的关键作用而受到极大关注。尽管在N-糖苷的构建方面取得了相当大的进展，但2-脱氧-α-N-糖苷的立体选择性构建方法仍然有限。

该文中，研究人员公开了在温和条件下镍催化的糖基化物的加氢胺化。这种转化可以立体选择性地合成具有优异的α-立体选择性的2-脱氧-α-N-糖苷阵列。镍催化的糖基化反应，特别是那些涉及异头C（sp3）-金属键形成的反应，已被证明是生产各种N-糖苷的有效和立体选择性策略。此外，着重介绍了该反应的应用，合成了γ-糖氨基酸衍生物。

附：英文原文

Title: Stereoselective Synthesis of 2-Deoxy-α-N-Glycosides from Glycals with 1,4,2-Dioxazol-5-ones

Author: Zhenpeng Shen, Guoyin Yin, Yangyang Li

Issue&Volume: 2024-05-07

Abstract: The synthesis of N-glycosides has received significant attention due to their crucial role in carbohydrate chemistry. Despite considerable advancements developed in the construction of N-glycosides, methods for the stereoselective construction of 2-deoxy-α-N-glycosides are still limited. Herein, we disclosed a nickel-catalyzed hydroamination of glycals under mild conditions. This transformation could allow for the stereoselective synthesis of an array of 2-deoxy-α-N-glycosides with excellent α-stereoselectivity. Nickel-catalyzed glycosylation reactions, particularly those involving anomeric C(sp3)-metal bond formation, have proven to be an effective and stereoselective strategy for producing various N-glycosides. Additionally, with highlight of the application of this reaction, γ-sugar amino acid derivatives were synthesized.

DOI: 10.1002/cjoc.202400224

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202400224