57830-00-9Relevant academic research and scientific papers
Rhodium-Catalyzed Intermolecular Silylation of Csp?H by Silacyclobutanes
He, Tao,Li, Bin,Liu, Lichuan,Ma, Wenpeng,He, Wei
supporting information, p. 5648 - 5652 (2021/03/08)
The signature reactivity of silacyclobutane (SCB) is their cycloaddition reactions with various π bonds. Recently, the first cases were disclosed where SCBs reacted with both Csp2?H and Csp3?H σ bonds in an intramolecular fashion. Herein, it is reported that SCB is also an efficient reagent for Csp?H bond silylation. Thus, rhodium-catalyzed intermolecular reactions between SCBs and terminal alkynes produced a series of symmetrical and unsymmetrical tetraorganosilicons bearing a Csp?Si functionality. Preliminary studies suggested that the reaction did not involve a cycloaddition pathway, but instead a direct activation of Csp?H bonds.
Cobalt-Catalyzed Defluorosilylation of Aryl Fluorides via Grignard Reagent Formation
Cho, Hyungdo,Cho, Seung Hwan,Jang, Minjae,Jeong, Jongheon,Kim, Hyunseok,Lee, Eunsung,Lim, Soobin
supporting information, p. 7387 - 7392 (2020/10/12)
Transition-metal-catalyzed transformations of the carbon-fluorine bond not only tackle an interesting problem of challenging bond activation but also offer new synthetic strategies where the relatively inert C-F bond is converted to versatile functional groups. Herein we report a practical cobalt-catalyzed silylation of aryl fluorides that uses a cheap electrophilic silicon source with magnesium. This method is compatible with various silicon sources and can be operated under aerobic conditions. Mechanistic studies support the in situ formation of a Grignard reagent, which is captured by the electrophilic silicon source.
Rhodium-Catalyzed Reaction of Silacyclobutanes with Unactivated Alkynes to Afford Silacyclohexenes
Chen, Hua,Chen, Yi,Tang, Xiaoxiao,Liu, Shunfa,Wang, Runping,Hu, Tianbao,Gao, Lu,Song, Zhenlei
supporting information, p. 4695 - 4699 (2019/03/07)
A Rh-catalyzed reaction of silacyclobutanes (SCBs) with unactivated alkynes has been developed to form silacyclohexenes with high chemoselectivity. Good enantioselectivity at the stereogenic silicon center was achieved using a chiral phosphoramidite ligand. The resulting silacyclohexenes are useful scaffolds for synthesizing structurally attractive silacyclic compounds.
Palladium-catalyzed desymmetrization of silacyclobutanes with alkynes: Enantioselective synthesis of silicon-stereogenic 1-sila-2-cyclohexenes and mechanistic considerations
Shintani, Ryo,Moriya, Kohei,Hayashi, Tamio
, p. 2902 - 2905 (2012/07/17)
A palladium-catalyzed enantioselective desymmetrization of silacyclobutanes with alkynes has been developed to give silicon-stereogenic 1-sila-2-cyclohexenes with high enantioselectivity. The products thus obtained undergo further derivatizations with complete stereoselectivity, and a new catalytic cycle involving alkyne coordination (oxidative cyclization)- transmetalation (σ-bond metathesis)-reductive elimination has also been proposed.
