17983-71-0Relevant academic research and scientific papers
Protodesilylation of Arylsilanes by Visible-Light Photocatalysis
García Manche?o, Olga,Kuhlmann, Jan H.,Uygur, Mustafa
supporting information, p. 1689 - 1694 (2022/03/14)
The first visible-light-mediated photocatalytic, metal- and base-free protodesilylation of arylsilanes is presented. The C(sp2)-Si bond cleavage process is catalyzed by a 5 mol % loading of a commercially available acridinium salt upon blue-light irradiation. Two simple approaches have been identified employing either aerobic or hydrogen atom transfer cocatalytic conditions, which enable the efficient and selective desilylation of a broad variety of simple and complex arylsilanes under mild conditions.
Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
Yamagishi, Hiroki,Saito, Hayate,Shimokawa, Jun,Yorimitsu, Hideki
, p. 10095 - 10103 (2021/08/18)
There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.
Ipso-Fluorination of aryltrimethylsilanes using xenon difluoride
Lothian, Aileen P.,Ramsden, Christopher A.,Shaw, Maxine M.,Smith, Rachel G.
, p. 2788 - 2793 (2011/05/02)
Reaction of aryltrimethylsilanes with xenon difluoride in C 6F6/Pyrex at room temperature gives aryl fluorides in good yield. The reaction is inhibited when acetonitrile is used as solvent but proceeds well in CFCl3/Pyrex or CH 2Cl2/Pyrex. Pyrex appears to be a very effective heterogeneous catalyst for this ipso-fluorination. The reaction does not proceed in PTFE, quartz, soda glass or glassy-carbon flasks or Pyrex flasks pre-rinsed with 2 M NaOH. Aryltrimethylstannanes and arylboronic acids and their esters do not undergo ipso-fluorination under similar conditions. Plausible mechanisms involving electrophilic addition of polarised xenon difluoride [FXeδ+?F→Pyrex δ-] followed by ligand coupling are discussed.
