Fu-Peng Wu

Palladium‐Catalyzed Ligand‐Controlled Selective Synthesis of Aldehydes and Acids from Aryl Halides and Formic Acid

Selective synthesis is in the core of modern organic chemistry. In this communication, a novel ligand‐dependent palladium‐catalyzed carbonylation procedure for the divergent synthesis of aldehydes and carboxylic acids from easily available aryl halides was established. Under the same reaction conditions, the reaction pathway could be controlled by the ligands applied to give formylated and carboxylated products selectively. Sterically hindered monodentate ligands facilitated the reductive carbonylation and provided aldehydes, whereas bidentate ligands preferred the carboxylation reaction and produced carboxylic acids. A wide range of functional groups were tolerated, and the products were, in general, obtained in moderate to excellent yields.

Direct Palladium-Catalyzed Carbonylative Transformation of Allylic Alcohols and Related Derivatives

A direct, palladium-catalyzed, carbonylative transformation of allylic alcohols for the synthesis of β,γ-unsaturated carboxylic acids has been developed. With formic acid as the CO source, various allylic alcohols were conveniently transformed into the corresponding β,γ-unsaturated carboxylic acids with excellent linear and (E)-selectivity. The reaction was performed under mild conditions; toxic CO gas manipulation and high-pressure equipment were avoided in this procedure.

Palladium-Catalyzed Carbonylative Transformation of Organic Halides with Formic Acid as the Coupling Partner and CO Source: Synthesis of Carboxylic Acids

A palladium-catalyzed carbonylative transformation of organic halides with formic acid as the coupling partner to produce carboxylic acids has been developed. With a catalytic amount of DCC as the activator of formic acid, the process can be realized successfully through benzoic formic anhydride as the intermediate. Both vinyl and aryl (pseudo)halides were conveniently transformed into the corresponding acids in good yields.

Palladium-catalyzed carbonylative Sonogashira coupling of aryl diazonium salts with formic acid as the CO source: the effect of 1,3-butadiene

An efficient carbonylative cross-coupling of aryl diazonium salts with terminal alkynes using formic acid as the CO source has been developed. Various useful alkynones were produced in moderate to good yields. Notably, 1,3-butadiene was found to play a crucial role in this transformation.

First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles

The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. The contents have been divided according to the electrophiles applied, followed by the different types of nucleophiles. Their reaction mechanisms and applications have been emphatically discussed.

Direct synthesis of benzylic amines by palladium-catalyzed carbonylative aminohomologation of aryl halides

Benzylic amines are valuable compounds with important applications in areas including pharmaceuticals and agrochemicals. The known procedures for their synthesis are limited by difficulties in functionalizing the parent aminomethyl groups. On the other hand, carbonylation reactions offer a potent method to introduce carbonyl groups and homologate carbon chains. However, carbonylative aminohomologation of aryl halides is challenging due to competing reactions and the need to balance multiple sequential steps. Here we report a palladium-catalyzed carbonylative aminohomologation reaction for the direct aminomethylation of aryl halides. The reaction proceeds via a tandem palladium-catalyzed formylation, followed by imine formation and formic acid-mediated reduction. Useful functional groups including chloride, bromide, ester, ketone, nitro, and cyano are compatible with this reaction. Both aryl iodides and bromides are suitable substrates and a wide range of synthetically useful amines are efficiently obtained in moderate to excellent yields.Palladium can catalyse both the reductive carbonylation of aryl halides to aldehydes, and the reductive amination of benzaldehydes with amines. Here the authors describe a tandem reductive carbonylation/reductive amination using carbon monoxide as the carbonyl source, constituting aminomethylation of aryl halides

Nickel-Catalyzed Carbonylative Synthesis of Functionalized Alkyl Iodides

Summary Functionalized alkyl iodides are important compounds in organic chemistry and biology. In this communication, we developed an interesting nickel-catalyzed carbonylative synthesis of functionalized alkyl iodides from aryl iodides and ethers. With Mo(CO)6 as the solid CO source, both cyclic and acyclic ethers were activated, which is also a challenging topic in organic synthesis. Functionalized alkyl iodides were prepared in moderate to excellent yields with outstanding functional group tolerance. Besides the high value of the obtained products, all the atoms from the starting materials were incorporated in the final products and the reaction had high atom efficiency as well.

Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of Benzophenones

A nickel-catalyzed molybdenum-promoted carbonylative coupling reaction for the synthesis of benzophenones from aryl iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO-gas-free conditions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.

Palladium‐Catalyzed Carbonylative Homocoupling of Aryl Iodides for the Synthesis of Symmetrical Diaryl Ketones with Formic Acid

A convenient method for the palladium‐catalyzed carbonylative homocoupling of aryl iodides was developed. With formic acid as the CO source, various symmetrical diaryl ketones were synthesized in moderate to good yield in the presence of a palladium catalyst.