35098-99-8Relevant 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.
9,10-Dihydro-9-sila-10-heteroanthracenes as new radical-based reducing agents
Oba, Makoto,Kawahara, Yoko,Yamada, Ryo,Mizuta, Hidetaka,Nishiyama, Kozaburo
, p. 1843 - 1848 (2007/10/03)
9,10-Dihydro-9-silaanthracenes 1 containing a heteroatom at the 10-position have been prepared and their reducing abilities for the reduction of some organic compounds under radical conditions have been investigated. Derivatives possessing a silicon, tin, oxygen or sulfur atom at the 10-position exhibited enhanced reactivities compared with the open-chain models. Among them, 9,10-dimethyl-9,10-dihydro-9,10-disilaanthracene 1a proved to be the most effective reagent for AIBN-initiated dehalogenation of organic halides and deoxygenation of aliphatic alcohols via O-thiocarbonyl derivatives. The rate constants for hydrogen abstraction from the Si-H moiety of these silaanthracenes 1 were determined using the neophyl rearrangement as a free radical clock in order to estimate their reactivities.
