4960-53-6Relevant academic research and scientific papers
Pd-Catalyzed reductive heck reaction of olefins with aryl bromides for Csp2-Csp3 bond formation
Jin, Liqun,Qian, Jiaxia,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
supporting information, p. 5752 - 5755 (2018/06/07)
We developed a Pd-catalyzed intermolecular reductive Heck reaction to construct Csp2-Csp3 bonds between aryl bromides and olefins. Various styrene derivatives, acyclic and cyclic alkenes, were well tolerated to couple with varied aryl bromides in linear selectivity. Kinetic and deuterium labeling experiments suggested that i-PrOH provides a hydride through β-H elimination.
Cation-π interactions in the gas phase methylation of α,ωdiphenylalkanes
Chiavarino, Barbara,Crestoni, Maria E.,Fornarini, Simonetta,Kuck, Dietmar
, p. 4619 - 4624 (2007/10/03)
The methylation of α,ω-diphenylalkanes (C6H5(CH2)nC6H5 , n = 1-6) has been performed in the gas phase using Me2Cl+ ions as alkylating species and toluene as reference substrate. Both in radiolytic experiments at atmospheric pressure and in FT-ICR measurements at 10-8 Torr, the selected diphenylalkanes reacted faster than toluene, the highest reactivity displayed by 1,3-diphenylpropane. The kinetic pattern of the reaction, conforming to the established scheme of an electrophilic alkylation reaction, is consistent with a rate-determining formation of the σ-complex intermediate, at variance with the tert-butylation of the same series of compounds by Me3C+ ions, occurring at the collisional encounter rate. The kinetic features are explained by a marked effect due to the presence of the second aryl ring, providing additional stabilization of both the ion-neutral collision complex and the σ complex with respect to toluene. Both factors contribute to the δEa of ca. 8 kcal mol-1 for the competition of 1,3-diphenylpropane and toluene found in the temperature dependence study of the Me2Cl+ reaction.
