Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
J Am Chem Soc. 2015 Sep 16;137(36):11586-9. doi: 10.1021/jacs.5b07384. Epub 2015 Sep 2.
Here, a palladium-catalyzed functionalization of unactivated sp(3) C-H bonds with internal alcohol nucleophiles is described. Directed by an oxime-masked alcohol, annulation chemoselectively occurs at the β position, leading to a range of aliphatic cyclic ethers with four- to seven-membered rings. Tethered primary, secondary, and tertiary free hydroxyl groups can all react to give the corresponding cyclized products. In addition, benzyl and silyl protected alcohols can also be directly coupled. An sp(3) C-H activation/intramolecular SN2 pathway was proposed.
在这里，描述了钯催化的未活化 sp(3) C-H 键与内醇亲核试剂的功能化。受肟掩蔽醇的导向，环化反应选择性地发生在β位，得到一系列具有四至七个环的脂肪族环醚。连有伯、仲和叔游离羟基的都能反应，得到相应的环化产物。此外，苄基和硅基保护的醇也能直接偶联。提出了 sp(3) C-H 活化/分子内 SN2 反应途径。
