无催化剂下醇和酚的高效O-硅基化

硅醚类化合物广泛应用于有机合成、 分离分析和精细化工等领域. 六甲基二氮硅烷是近年来发展的一种新型硅基化试剂, 被用于硅醚的高效合成, 但由于六甲基硅烷较为惰性, 通常需要加入催化剂活化. 本文报道了一种无催化剂下醇、 酚的高效硅基化新方法. 研究结果表明, 该方法可以兼容一级苄醇、 杂芳基苄醇、 脂肪醇, 二级醇甚至三级醇, 多数反应可以实现定量转化, 无需柱层析即可实现产物的分离纯化. 该方法可以拓展到酚的高效硅醚化, 也可以很方便地放大到100 mmol, 收率达到99%, 表明该方法具有较好的实用价值.

Catalyst-free and Highly Efficient O-Silylation of Alcohols and Phenols

Silyl ethers are widely used in many fields such as organic synthesis， separation analysis， fine chemicals， etc. Hexamethyldiazosilane（HMDS） was recently developed as a new silyl reagent for the efficient synthesis of silyl ethers. However， a catalyst was usually required to activate the inert HMDS. In this work， an efficient and catalyst-free O-Silylation of alcohols and phenols was developed. This new method could be successfully applied to a variety of primary benzyl alcohols， heteroaryl benzyl alcohols， aliphatic alcohols， secondary alcohols and even tertiary alcohols. In Most cases， the target product was obtained under column chromatography-free conditions with a quantitative isolated yield. This method can be extended to the highly efficient O-Silylation of phenols， and also be easily scaled up to 100 mmol， giving the target product in 99% isolated yield， indicating that this new method is of good practical value.