Nagamalla Someshwar, Dhokale Ranjeet A, Seidl Frederick J, Mague Joel T, Sathyamoorthi Shyam
Department of Medicinal Chemistry, University of Kansas, Lawrence, Kansas, United States, 66047.
Independent Researcher, San Mateo, California, United States, 94402.
Org Chem Front. 2021 Oct 7;8(19):5361-5368. doi: 10.1039/d1qo01008e. Epub 2021 Aug 3.
We present the first examples of rearrangement reactions of allylic silanol substrates into linear ketone and 5-membered cyclic silanediol organomercurial products. Both reactions are mediated by Hg(OTf) but differ in the use of base, solvent, and temperature. The substrate scope of both transformations was explored, and the product organomercurials were shown to be valuable synthons. Mechanistic studies suggest that both products are the result of a series of transformations, cascading in one pot. DFT analysis provides a basis for understanding the rearrangement of a 6- intermediate into the 5- cyclic silanediol product.
我们展示了烯丙基硅醇底物重排反应生成线性酮和五元环硅二醇有机汞产物的首个实例。这两种反应均由三氟甲磺酸汞介导，但在碱的使用、溶剂和温度方面有所不同。我们探索了这两种转化反应的底物范围，并表明产物有机汞是有价值的合成子。机理研究表明，这两种产物都是一系列转化反应在一锅法中串联进行的结果。密度泛函理论（DFT）分析为理解六元中间体重排为五元环硅二醇产物提供了依据。
