Palladium-catalyzed arylation of methyl vinyl ether

Direct Synthesis of Protected Arylacetaldehydes by Tetrakis(phosphane)palladium‐Catalyzed Arylation of Ethyleneglycol Vinyl Ether

“…[7] Nevertheless, the arylation of electron-rich olefins such as enol ethers is often limited by poor α/β regioselectivity. [8][9][10][11][12] Highly α-regioselective arylations in the presence of n-butyl vinyl ether have been reported by Cabri et al and Hallberg et al in the presence of Pd(OAc) 2 / dppp. [13][14][15][16] In some procedures, TlOAc was added in order to improve the regioselectivity of the reaction.…”

Intermolecular Heck Reaction: Scope, Mechanism, and Other Fundamental Aspects of the Intermolecular Heck Reaction

“…Taking the arylation of alkyl vinyl ethers as an example, the regioselectivity is directed strongly by the electronic properties of the aromatic substrate, the counterion in the oxidative addition complex, the presence or absence of phosphine ligands, and the solvent. [76], [84]- [86] Cabri and co-workers discovered that bidentate phosphine ligands promote internal (␣-)arylations of heteroatom-substituted alkenes and allylic substrates with very high selectivity. [33]- [35] For this observation Cabri and Candiani proposed a mechanistic rationale in which two different pathways for the coordination-insertion process were taken into account (Schemes 11 and 12).…”

Bimetallic Substituted Ceria: An Alternative Approach to Ligand-Free Heck-Mizoroki Cross-Coupling Reactions

“…Substituents with electron-withdrawing groups It is important to note the various stages at which each substrates is involved in the reaction, in order to better understand the relationships observed. Aryl halides are involved in the oxidative addition step that is governed by the reactivity of the C-X bond [59,70,71]. Thus, an electron-withdrawing group should decrease the reactivity of the C-X bond, increasing the rate of the oxidation step, since the C-X bond does not get polarised, as is the case for the electron-donating substrates.…”