Pacheco João A, Candeias Nuno R
LAQV REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal.
Faculty of Engineering and Natural Sciences, Tampere University, Korkeakoulunkatu 8, 33101, Tampere, Finland.
Angew Chem Int Ed Engl. 2024 Dec 9;63(50):e202414424. doi: 10.1002/anie.202414424. Epub 2024 Nov 6.
Carbohydrates constitute the largest source of biomass on Earth, but their synthetic modification is challenging due to their high content in oxygen functionalities. The site- and stereoselective modification of native sugars is a definite goal of glycochemistry research. Recent efforts to bypass the need for protecting groups, leveraging selective activation through photochemical mechanisms for site-selective C-C bond formation from native sugars, are likely to largely impact all glycochemistry-related areas. Davis, Koh, and co-workers have recently presented their use of photocatalysis to develop a "cap and glycosylate" approach for the site- and stereoselective C-glycosylation of native sugars. A modernized direct radical functionalization of in situ formed thioglycoside using photocatalysis was used in the synthetic manipulation of unprotected carbohydrates. This allowed reaching complex saccharides, and post-translational modification of proteins.
碳水化合物是地球上最大的生物质来源，但由于其氧官能团含量高，对其进行合成修饰具有挑战性。天然糖类的位点和立体选择性修饰是糖化学研究的一个明确目标。最近，人们努力绕过对保护基团的需求，利用光化学机制进行选择性活化，以实现天然糖类的位点选择性碳-碳键形成，这可能会对所有与糖化学相关的领域产生重大影响。戴维斯、 Koh 及其同事最近展示了他们利用光催化开发一种 “封端并糖基化” 的方法，用于天然糖类的位点和立体选择性碳糖基化。利用光催化对原位形成的硫代糖苷进行现代化的直接自由基官能化，用于未保护碳水化合物的合成操作。这使得能够合成复杂的糖类，并对蛋白质进行翻译后修饰。
