Reductive formylation of aromatic halides under low carbon monoxide pressure catalyzed by transition-metal compounds

Mild, Redox‐Neutral Formylation of Aryl Chlorides through the Photocatalytic Generation of Chlorine Radicals

“…[4] Although this procedure has been performed on multi-ton scale, [5] the conditions are not ideal for benchtop synthesis due to the hazards associated with carbon monoxide and the specialized equipment required for handling high pressure syngas. To develop user-friendly protocols, several laboratories have reported alternative condensed phase reductants [6] and CO surrogates [7] such as the crystalline N ‐formylsaccharin. [7b] Nevertheless, reductive formylations are still limited to simple arenes due to the general requirements of high reaction temperatures and stoichiometric reducing agents.…”

Tetrakis(triphenylphosphine)palladium(0)

“…121 Other vinyl epoxides, such as those in open chains or in cyclic systems in which the double bond is not in the ring, are converted under similar conditions into dienols. (47) O O Pd(Ph 3 P) 4 , Ph 3 P…”

Carbonylation and Decarbonylation Reactions

“…Methyl aryl ketones can be synthesized via carbonylation of aryl iodides and tetramethyltin in the presence of a nickel catalyst (equation 14). 26 Unfortunately the reaction cannot be extended to the synthesis of unsymmetrical diaryl ketones since tetraphenyltin does not react under these conditions.…”