4043-71-4Relevant articles and documents
Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle
Woof, Callum R.,Durand, Derek J.,Fey, Natalie,Richards, Emma,Webster, Ruth L.
supporting information, p. 5972 - 5977 (2021/03/17)
Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H3N?BH3). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η2-coordinated alkene FeI complex, followed by oxidative addition of the alkene to give an FeIII intermediate, which then undergoes reductive elimination to allow release of the isomerization product.
Nickel-Catalyzed Allylic C(sp2)–H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes
Wu, Qiang,Wang, Lanlan,Jin, Rizhe,Kang, Chuanqing,Bian, Zheng,Du, Zhijun,Ma, Xiaoye,Guo, Haiquan,Gao, Lianxun
, p. 5415 - 5422 (2016/11/22)
Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp2)–H activation by in-situ-formed Ni0, which is inserted into the C–H bond at the 2-position of the allyl moiety without a directing group. The isomerization of allylarene to 1-propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross-coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp2)–H activation and represents a new method for the synthesis of 1,1-disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp2)–H activation and multiple intermolecular 1,2-, 1,3-, and 2,3-hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.
Rhodium catalyzed aqueous biphasic hydroformylation of naturally occurring allylbenzenes in the presence of water-soluble phosphorus ligands
Baricelli, Pablo J.,Rodriguez, Mariandry,Melean, Luis G.,Alonso, Maria Modro?o,Borusiak, Margarita,Rosales, Merlin,Gonzalez, Beatriz,De Oliveira, Kelley C. B.,Gusevskaya, Elena V.,Dos Santos, Eduardo N.
, p. 163 - 169 (2015/05/05)
The rhodium-catalyzed hydroformylation of eugenol was performed in aqueous biphasic systems using various water soluble phosphines: TPPTS (triphenylphosphinetrisulphonated); BDPPETS (bisdiphenylphosphinoethanetetrasulphonated), BDPPPTS (bisdiphenylphosphi