1393446-11-1Relevant academic research and scientific papers
Ruthenium-Catalyzed Site-Selective Intramolecular Silylation of Primary C-H Bonds for Synthesis of Sila-Heterocycles
Fang, Huaquan,Hou, Wenjun,Liu, Guixia,Huang, Zheng
supporting information, p. 11601 - 11609 (2017/08/30)
Incorporating the silicon element into bioactive organic molecules has received increasing attention in medicinal chemistry. Moreover, organosilanes are valuable synthetic intermediates for fine chemicals and materials. Transition metal-catalyzed C-H silylation has become an important strategy for C-Si bond formations. However, despite the great advances in aromatic C(sp2)-H bond silylations, catalytic methods for aliphatic C(sp3)-H bond silylations are relatively rare. Here we report a pincer ruthenium catalyst for intramolecular silylations of various primary C(sp3)-H bonds adjacent to heteroatoms (O, N, Si, Ge), including the first intramolecular silylations of C-H bonds α to O, N, and Ge. This method provides a general, synthetically efficient approach to novel classes of Si-containing five-membered [1,3]-sila-heterocycles, including oxasilolanes, azasilolanes, disila-heterocycles, and germasilolane. The trend in the reactivity of five classes of C(sp3)-H bonds toward the Ru-catalyzed silylation is elucidated. Mechanistic studies indicate that the rate-determining step is the C-H bond cleavage involving a ruthenium silyl complex as the key intermediate, while a η2-silene ruthenium hydride species is determined to be an off-cycle intermediate.
Synthesis of phenols via fluoride-free oxidation of arylsilanes and arylmethoxysilanes
Rayment, Elizabeth J.,Summerhill, Nick,Anderson, Edward A.
experimental part, p. 7052 - 7060 (2012/10/07)
Rapid, efficient methods have been developed to prepare phenols from the oxidation of arylhydrosilanes. The effects of arene substituents and fluoride promoters on this process show that while electron-deficient arenes can undergo direct oxidation from the hydrosilane, electron-rich aromatics benefit from silane activation via oxidation to the methoxysilane using homogeneous or heterogeneous transition metal catalysis. The combination of these two oxidations into a streamlined flow procedure involving minimal processing of reaction intermediates is also reported.
