P(v) intermediate-mediated E1cB elimination for the synthesis of glycals.

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 ^t BuONa/D₂O-hydrolysis-elimination. Mechanistic investigations indicated that the oxaphosphorane intermediate-mediated E1cB mechanism is responsible for the elimination reaction.

SUBMITTER: Liu F 

PROVIDER: S-EPMC9116453 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature