1252259-63-4Relevant academic research and scientific papers
Rhodium-Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9-Sila- and 9-Germafluorenes: A Combined Experimental and Computational Mechanistic Study
Murai, Masahito,Okada, Ryo,Asako, Sobi,Takai, Kazuhiko
, p. 10861 - 10870 (2017)
Stoichiometric amounts of oxidants are widely used as promoters (hydrogen acceptors) in dehydrogenative silylation of C?H bonds. However, the present study demonstrates that silylative and germylative cyclization with dehydrogenation can proceed efficiently, even without hydrogen acceptors. The combination of [RhCl(cod)]2 and PPh3 was effective for both transformations, and allowed a reduction in reaction temperature compared with our previous report. Monitoring of the reactions revealed that both transformations had an induction period for the early stage, and that the rate constant of dehydrogenative germylation was greater than that of dehydrogenative silylation. Competitive reactions in the presence of 3,3-dimethyl-1-butene indicated that the ratio of dehydrogenative metalation and hydrometalation was affected by reaction temperature when a hydrosilane or hydrogermane precursor was used. Further mechanistic insights of oxidant-free dehydrogenative silylation, including the origin of these unique reactivities, were obtained by density functional theory studies.
Rhodium-catalyzed dehydrogenative germylation of C-H bonds: New entry to unsymmetrically functionalized 9-germafluorenes
Murai, Masahito,Matsumoto, Koji,Okada, Ryo,Takai, Kazuhiko
, p. 6492 - 6495 (2015/02/19)
Rhodium-catalyzed dehydrogenative germylation leading to unsymmetrically functionalized 9-germafluorenes via Ge-H and C-H bond activation is described. Despite the significant achievements made in dehydrogenative functionalization of C-H bonds, only a limited number of examples with the fourth-row atom-H bonds have been reported. The current method enabled the synthesis of various 9-germafluorene derivatives, including tetracyclic as well as donor-acceptor substituted germoles, which may be useful for electronic device applications.
Rhodium-catalyzed synthesis of silafluorene derivatives via cleavage of silicon-hydrogen and carbon-hydrogen bonds
Ureshino, Tomonari,Yoshida, Takuya,Kuninobu, Yoichiro,Takai, Kazuhiko
supporting information; experimental part, p. 14324 - 14326 (2010/12/19)
The rhodium-catalyzed synthesis of silafluorenes from biphenylhydrosilanes is described. This highly efficient reaction proceeds via both Si-H and C-H bond activation, producing only H2 as a side product. Using this method, a ladder-type bis-silicon-bridged p-terphenyl could also be synthesized.
