Lind Florian, Markelov Kirill, Studer Armido
Organisch-Chemisches Institut, Universität Münster Corrensstrasse 40 48149 Münster Germany
Chem Sci. 2023 Oct 25;14(44):12615-12620. doi: 10.1039/d3sc04975b. eCollection 2023 Nov 15.
Silyl chlorides are highly valuable and popular reagents for the protection of alcohols. In this edge article we introduce a photocleavable alcohol protecting group on the basis of acyl silanes. To achieve this, acylchlorosilanes that represent a new class of acylsilanes were developed. They can be easily synthesized in a concise sequence of three steps in high overall yield. Alcohol silyl protection takes place under established mild conditions, akin to those associated with classical silicon-based protecting groups. The removal of the Si-group is achieved at room temperature through exposure to visible light (456 nm) in methanol. We demonstrate a broad spectrum of substrates with remarkable tolerance toward diverse functional groups, highlighting a substantial level of orthogonality with respect to other protecting groups. Furthermore, we showcase the robustness of this approach against various transformations.
硅氯化合物是用于保护醇类的非常有价值且常用的试剂。在这篇前沿文章中，我们基于酰基硅烷引入了一种可光裂解的醇保护基。为此，开发了一类新型酰基硅烷——酰氯硅烷。它们可以通过简洁的三步反应轻松合成，总产率很高。醇的硅基保护在既定的温和条件下进行，类似于与传统硅基保护基相关的条件。通过在甲醇中暴露于可见光（456 nm），在室温下即可实现硅基的去除。我们展示了一系列对各种官能团具有显著耐受性的底物，突出了其与其他保护基的高度正交性。此外，我们展示了这种方法在各种转化反应中的稳健性。
