Stereoselective Synthesis of 2-Deoxy-β-O-Aryl Glycosides by a One-Pot Strategy Involving C─O Coupling and
Yang-He Wang1, You-Hong Niu1, Qin Li1
1State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, Xue Yuan Road No. 38, Beijing, 100191, China.
Abstract:
Naturally occurring 2-deoxy-β-O-aryl glycosides are an important class of anticancer and antibacterial compounds. The direct glycosylation of phenols inevitably produces 2-deoxy-α-O-aryl glycosides, decreasing the efficiency of the synthesis of 2-deoxy-β-O-aryl glycosides. Herein we report a novel one-pot approach for the synthesis of 2-deoxy-β-O-aryl glycosides by the Cu(I)-catalyzed C─O cross-coupling reaction of 1-iodoglycals and phenols, followed by in situ reduction of the obtained ketene acetals with catecholborane. Starting from readily available materials, this protocol is applicable to a wide range of substrates, affording the corresponding 2-deoxy-β-O-aryl glycosides in high yields and with exclusive β-stereoselectivity. This strategy was further applied to the late-stage modification of various bioactive natural products or drugs. The remarkable stereoselectivity was rationalized by the experimental and theoretical studies.
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