Pd‐Catalyzed Vinylation of Aryl Halides with Inexpensive Organosilicon Reagents Under Mild Conditions

Abstract

Pd-catalyzed Hiyama vinylation reaction of non-activated aryl chlorides and bromides under mild conditions was developed. The use of efficient vinyl donors and electron-rich sterically hindered phosphine ligands was critical for the success of the reaction. The products of this transformation can be used for Am/Cm separation, an important challenge in nuclear fuel reprocessing. The substituent effect on Am/Cm separating selectivity was also achieved, which could contribute to the development of new chromatographic materials for the separation of Am and Cm.

Mechanistic Study of Palladium-Catalyzed Hydroesterificative Copolymerization of Vinyl Benzyl Alcohol and CO

“…There are several plausible pathways for the loss of propagating functional groups in this reaction. First, as mentioned previously, alcohol oxidation is a common pathway of activation in Pd-catalyzed hydroesterification reactions. ,, Indeed, small peaks at ∼10 ppm, consistent with the formation of aldehydes, are observable in the 1 H NMR spectrum of crude reaction mixtures. Multiple peaks are observed, including 4-vinylbenzaldehyde, likely indicating that both monomeric and polymeric alcohol moieties are oxidized.…”

Nickel-Catalyzed Ligand-Free Hiyama Coupling of Aryl Bromides and Vinyltrimethoxysilane

“…2-methoxy-6-vinylnaphthalene (3a) [1] The reaction was performed following GP2. White solid, 30.2 mg, yield: 82%.…”

“…White solid, 21.1 mg, yield: 66%. phenyl(4-vinylphenyl)methanone (3n, known compound) [1] The reaction was performed following GP2. White solid, 35.0 mg, yield: 84%.…”

“…Colorless liquid, 22.2 mg, yield: 85%. 1-(methylsulfonyl)-4-vinylbenzene (3q) [1] The reaction was performed following GP2. Colorless liquid, 27.0 mg, yield: 75%.…”

“…Styrene derivatives represent one of the most important structural units in organic chemistry. Moreover, they serve as versatile synthetic intermediates in various organic transformations, such as olefin metathesis 1 , Heck reaction 2 , hydrofunctionalization 3 , and epoxidation 4 . Besides, they are widely used as monomers for polymer synthesis.…”