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钌(II)催化远程 C-H 糖苷化反应:间位 C-芳基糖苷的模块化组装。

Remote C-H Glycosylation by Ruthenium(II) Catalysis: Modular Assembly of meta-C-Aryl Glycosides.

机构信息

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammanstraße 2, 37077, Göttingen, Germany.

Wöhler Research Institute for Sustainable Chemistry, Tammanstraße 2, 37077, Göttingen, Germany.

出版信息

Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202208620. doi: 10.1002/anie.202208620. Epub 2022 Sep 13.

Abstract

The prevalence of C-aryl glycosides in biologically active natural products and approved drugs has long motivated the development of efficient strategies for their selective synthesis. Cross-couplings have been frequently used, but largely relied on palladium catalyst with prefunctionalized substrates, while ruthenium-catalyzed C-aryl glycoside preparation has thus far proven elusive. Herein, we disclose a versatile ruthenium(II)-catalyzed meta-C-H glycosylation to access meta-C-aryl glycosides from readily available glycosyl halide donors. The robustness of the ruthenium catalysis was reflected by mild reaction conditions, outstanding levels of anomeric selectivity and exclusive meta-site-selectivity.

摘要

C-芳基糖苷在具有生物活性的天然产物和已批准药物中的普遍性长期以来一直激发了对其选择性合成的有效策略的发展。交叉偶联反应经常被使用,但主要依赖于带有预官能化底物的钯催化剂,而钌催化的 C-芳基糖苷制备迄今为止一直难以实现。在此,我们披露了一种通用的钌(II)催化的间位 C-H 糖苷化方法,可从易得的糖基卤化物供体中获得间位 C-芳基糖苷。钌催化的稳健性反映在温和的反应条件、出色的端基选择性和专有的间位选择性上。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/00b2/9825995/d28d27eebddd/ANIE-61-0-g004.jpg

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