摘要：The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, China; State Key Laboratory of Coordination Chemistry, S

转自：康龙化成

Stereoselective Synthesis of Glycomimetics by Photocatalytic One-Pot C(sp3)─H Acylation and Ring Contraction

Zhijun Zhou+, Yuqi Ai+, Sheng Xu, Xinjing Lin, Yuanyuan Ping,* and Wangqing Kong*

The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, China; State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

—Angew. Chem. Int. Ed. 2025, e202510594

KEYWORDS:Photo chemistry, C─H Acylation, Ring contraction, Ni catalysis (反应类型), 1-deoxyglycosides (原料), C-acyl glycosides, carbasugars, Glycomimetics (产物), C(sp3)-C=O (成键类型)

ABSTRACT: Glycomimetics, structural mimics of natural carbohydrates such as C-glycosides and carbasugars, are important therapeutic leads for treating a variety of diseases. However, the structural and stereochemical complexity of glycomimetics poses daunting challenges to synthetic chemists and is incompatible with diversity-oriented synthetic approaches. Herein, we develop a facile and general method for the stereoselective synthesis of C-acyl glycosidesand carbasugarsfrom readily accessible and stable 1-deoxyglycosides via photo-HAT/nickel dual catalysis. The reaction proceeds in one-pot under mild conditions and exhibits high stereoselectivity across a wide range of glycosyl units, illustrating the potential of this method in the preparation of structurally diverse and densely functionalized carbasugars. The synthetic utility of this strategy is further demonstrated in the synthesis of challenging cyclopentanepentol, an analogue of calditol.

Background:The significance of carbohydrate mimetics and their synthesis strategies

Substrate Scope: One-pot C(sp3) ─H acylation/ring contraction for the stereoselective synthesis of carbasugars

Proposed Mechanism

Prof. Wangqing Kong and co-worker reportedhere a photo-HAT/nickel dual-catalyzed stereoselective C(sp3)─H acylation of 1- deoxyfuranoses with acyl chlorides, providing an efficient strategy for the stereoselective synthesis of C-acyl glycosides. We have also developed a one-pot cascade C(sp3)─H acylation and ring contraction for the rapid and stereoselective synthesis of carbasugars. Taking advantage of the easy accessibility of 1-deoxyglycosides and the possibility of prior structural modification, the reaction proceeds in one-pot under mild conditions, demonstrating the potential of this approach for the preparation of structurally diverse and densely functionalized glycomimetics. Moreover, the synthetic utility of this strategy is further illustrated in the stereoselective synthesis of cyclopentanepentol, an analogue of calditol.

来源：新浪财经