18406-01-4Relevant articles and documents
Light-Promoted Transfer of an Iridium Hydride in Alkyl Ether Cleavage
Fast, Caleb D.,Schley, Nathan D.
supporting information, p. 3291 - 3297 (2021/10/12)
A catalytic, light-promoted hydrosilylative cleavage reaction of alkyl ethers is reported. Initial studies are consistent with a mechanism involving heterolytic silane activation followed by delivery of a photohydride equivalent to a silyloxonium ion generated in situ. The catalyst resting state is a mixture of Cp*Ir(ppy)H (ppy = 2-phenylpyridine-κC,N) and a related hydride-bridged dimer. Trends in selectivity in substrate reduction are consistent with nonradical mechanisms for C-O bond scission. Irradiation of Cp*Ir(ppy)H with blue light is found to increase the rate of hydride delivery to an oxonium ion in a stoichiometric test. A comparable rate enhancement is found in carbonyl hydrosilylation catalysis, which operates through a related mechanism also involving Cp*Ir(ppy)H as the resting state.
Mild synthesis of silyl ethers: Via potassium carbonate catalyzed reactions between alcohols and hydrosilanes
Delucia, Nicholas A.,Das, Nivedita,Vannucci, Aaron K.
, p. 3415 - 3418 (2018/05/23)
A method has been developed for the silanolysis of alcohols using an abundant and non-corrosive base K2CO3 as a catalyst. Reactions between a variety of alcohols and hydrosilanes generate silyl ethers under mild conditions. The use of hydrosilanes leads to the formation of H2 as the only byproduct thus avoiding the formation of stoichiometric strong acids. The mild conditions lead to a wide scope of possible alcohol substrates and good functional group tolerance. Selective alcohol silanolysis is also observed in the presence of reactive C-H bonds, lending this method for extensive use in protection group chemistry.
Activation of silanes by Grubbs' carbene complex Cl2(PCy3)2Ru=CHPh: Dehydrogenative condensation of alcohols and hydrosilylation of carbonyls
Maifeld, Sarah V,Miller, Reagan L,Lee, Daesung
, p. 6363 - 6366 (2007/10/03)
This manuscript describes two catalytic methods for silyl ether synthesis using Grubbs' catalyst Cl2(PCy3)2Ru=CHPh. Silyl ethers are obtained from the reaction of a variety of silanes with alcohols by dehydrogenative conde
