Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588-0304, United States.
Org Lett. 2014 Oct 17;16(20):5235-7. doi: 10.1021/ol502726p. Epub 2014 Oct 6.
Alkyl tetrahydropyranyl peroxides (ROOTHP) transfer alkoxide (OR) to lithiated 1,3-dithianes. The derived S,S,O-orthoesters undergo fluorodesulfurization with HF/pyridine and N-bromosuccinamide (NBS) to furnish difluoromethyl ethers. The overall protocol can be applied to synthesis of both terminal (ROCF2H) and internal (ROCF2R') ethers. Application of the same set of reactions to a lithiated tris(alkylthio)alkane is shown to generate a trifluoromethyl ether.
烷基四氢吡喃过氧化物 (ROTHP) 将烷氧基 (OR) 转移到连有锂的 1,3-二噻烷上。得到的 S,S,O-缩醛在 HF/吡啶和 N-溴代丁二酰亚胺 (NBS) 的作用下进行氟代脱硫反应，生成二氟甲基醚。整个方案可应用于末端 (ROCF2H) 和内部 (ROCF2R') 醚的合成。同样的反应体系应用于连有锂的三(烷基硫代)烷烃，生成三氟甲基醚。
