1191-96-4Relevant articles and documents
Liquid-phase noncatalytic butene oxidation with nitrous oxide
Semikolenov,Dubkov,Starokon',Babushkin,Panov
, p. 948 - 956 (2005)
The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation energies and have the first orders with respect to the alkene and N2O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation of terminal and internal alkenes C 2-C8 with nitrous oxide were analyzed using the previously published data.
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.
A Photochemical Source of Real Alkylcarbenes
Glick, HC,Likhotvorik, Igor R.,Jones, Maitland
, p. 5715 - 5718 (2007/10/02)
Treatment of 7,7-dibromodibenzobicycloheptane with di-tert-butylcuprate or dibutylcuprate, followed by quenching with water, led to exo- and endo-7-monoalkyldibenzobicycloheptanes.Photolysis through either quartz or Pyrex gave the products of intramolecular reactions of the corresponding alkylcarbenes.The temperature dependence of the products formed from tert-butylcarbene was verified, and butylcarbene was trapped intermolecularly. - Keywords: carbenes, retrocycloadditions, insertion reactions.
