2412-81-9Relevant academic research and scientific papers
Highly selective formation of linear esters from terminal and internal alkenes catalysed by palladium complexes of bis-(di-tert-butylphosphinomethyl) benzene
Rodriguez, Cristina Jimenez,Foster, Douglas F.,Eastham, Graham R.,Cole-Hamilton, David J.
, p. 1720 - 1721 (2007/10/03)
The methoxycarbonylation of terminal or internal alkenes catalysed by palladium complexes of bis-(di-tert-butylphosphinomethyl)benzene under mild conditions leads to linear esters in 99% selectivity via a hydride mechanism.
The Reactivity of Carbenes from Photolysis of Diazo-Compounds towards Carbon-Hydrogen Bonds. Effects of Structure, Temperature, and Matrix on the Insertion Selectivity
Tomioka, Hideo,Itoh, Masami,Yamakawa, Shyoji,Izawa, Yasuji
, p. 603 - 609 (2007/10/02)
Direct and/or sensitized photolyses of diazo-acetate (1a) and -malonate (1b) in hydrocarbons and ether were investigated at various temperatures in order to learn more about the nature of the C-H insertion process and the structural factors governing positional selectivity within the matrix.Photolysis of the diazo-compounds in a rigid matrix resulted in a marked decrease in the insertion selectivity, which may be interpreted as indicating that the matrix imposes severe steric demand especially on the direct C-H insertion process of the singlet carbene.The addition of a sensitizer in matrix photolysis causes a marked increase in the selectivity in the case of (1a), as is observed in the comparable liquid-phase experiment, but it causes a decrease in the case of (1b).This is interpreted as suggesting that the excited triplet (1b) itself is involved in C-H insertion under these conditions.More extensive temperature studies show that, as the temperature decreases, the C-H insertion selectivity of :CHCO2R decreases regularly regardless of the reaction phase, whereas that of :C(CO2R)2 increases in the liquid phase but decreases in the solid phase.This difference in the temperature dependence is explained by assuming that the singlet carbene is responsible for the C-H insertion of :CHCO2R throughout the temperature range studied, while both singlet and triplet are involved in the insertion of :C(CO2R)2.
