P(v) intermediate-mediated E1cB elimination for the synthesis of glycals |
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Authors: | Fen Liu Haiyang Huang Longgen Sun Zeen Yan Xiao Tan Jing Li Xinyue Luo Haixin Ding Qiang Xiao |
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Affiliation: | Key Laboratory of Organic Chemistry, Institute of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013 Jiangxi Province China, |
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Abstract: | Glycals are highly versatile and useful building blocks in the chemistry of carbohydrate and natural products. However, the practical synthesis of glycals remains a long-standing and mostly unsolved problem in synthetic chemistry. Herein, we present an unprecedented approach to make a variety of glycals using phosphonium hydrolysis-induced, P(v) intermediate-mediated E1cB elimination. The method provides a highly efficient, practical and scalable strategy for the synthesis of glycals with good generality and excellent yields. Furthermore, the strategy was successfully applied to late-stage modification of complex drug-like molecules. Additionally, the corresponding 1-deuterium-glycals were produced easily by simple tBuONa/D2O-hydrolysis–elimination. Mechanistic investigations indicated that the oxaphosphorane intermediate-mediated E1cB mechanism is responsible for the elimination reaction.A novel glucosylphosphonium-hydrolysis induced E1cB-elimination provides a highly efficient, practical and scalable method for the synthesis of glycals with good compatibility and excellent yields. |
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