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.

中文翻译：

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P(V) 中间体介导的 E1cB 消除用于合成糖醛

Glycals 是碳水化合物和天然产物化学中用途广泛且有用的组成部分。然而，糖醛的实际合成仍然是合成化学中长期存在且大部分未解决的问题。在这里，我们提出了一种前所未有的方法来使用磷水解诱导的 P( V ) 中间体介导的 E1cB 消除来制作各种糖醛。该方法为糖醛的合成提供了一种高效、实用和可扩展的策略，具有良好的通用性和优异的收率。此外，该策略成功应用于复杂类药物分子的后期修饰。^{此外，通过简单的t} BuONa/D ₂很容易产生相应的 1-氘-糖苷O-水解-消除。机理研究表明，氧杂膦中间体介导的 E1cB 机制负责消除反应。