Palladium or nickel-catalyzed benzoylation and phenylation of methyl acrylate

Transition‐Metal‐Catalyzed Decarbonylative Coupling Reactions: Concepts, Classifications, and Applications

“…Mizoroki-Heck cross-coupling has found extensive application in transformationst hat do not require stoichiometrica mounts of organometallic reagents for the desired carbon-carbon bond formation, which is am ajor advantage compared with other cross-coupling procedures.A se arly as in the late 1970s, chemists conducted investigationso nt he Ni-or Pd-catalyzed Mizoroki-Heck reaction of aroyl chlorides with methyl acrylate, and observed the formation of decarbonylative couplingp roduct. [19] Later on, Spencer and Miura independently extended the Mizoroki-Heck-type decarbonylative methodology with variousa royl chlorides and olefins to palladium and rhodium catalysis. [20] In 1998, de Vries and co-workersd eveloped aH eck-type decarbonylative olefination of anhydrides with terminal and internal alkenes.…”

Carboxylic acid chlorides as arylating agents in the palladium-catalyzed Heck reaction - The Blaser reaction

“…12 Assim, diferentemente da reação de Heck com halogenetos de arila como eletrófilos, esta reação se processa sem a necessidade da adição de fosfinas, as quais inibem o processo de migração do monóxido de carbono. 30 Adicionalmente, são empregados solventes apolares e bases volumosas a fim de evitar que estes atuem como ligantes, impedindo a migração de CO. Spencer e Blaser relataram que hidrocarbonetos aromáticos conduziram aos melhores resultados. 29 A velocidade da reação de Heck descarbonilativa diminui com o tempo.…”

Nickel Catalyzed Coupling of Organic Halides and Related Reactions

“…134 The catalytic activity of the phosphine modified catalysts is apparently more dependent upon the structure of the Grignard reagent than upon that of the organic halide and results for a selection of ligands are shown in Table 4. 149 Reduction is also observed on treating allyl alcohols with «-propylmagnesium bromide 132 and has been used in the stereospecific conversion of tetrasubstituted alkoxysilanes into trisubstituted silanes (equation 82 The coupling reaction proceeds readily with aryl, alkynyl, alkenyl and allyl halides and that with aryl halides has been extended to polyhalobenzene, condensed aromatic compounds and sterically hindered systems (equations [83][84][85][86][87]. However in some cases, e.g.…”