Jin-Bao Peng

Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers.

Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied. In this manuscript, the recent achievements in using organic dyes as visible-light sensitizers in carbonylation chemistry are summarized and discussed.

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.

Ligand- and Solvent-Controlled Regio- and Chemodivergent Carbonylative Reactions

The development of highly selective procedures is one of the core goals in organic chemistry. Among the known organic transformations, carbonylation reactions present an ideal choice for the preparation of carbonyl-containing compounds. In this review, the recent achievements on the control of the selectivity for carbonylation reactions have been summarized. The effects of ligands, solvents, and bases on the selectivity are been discussed.

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.

Convenient and General Zinc-Catalyzed Borylation of Aryl Diazonium Salts and Aryltriazenes under Mild Conditions

Abstract A convenient and general zinc‐catalyzed borylation of aryl diazonium salts and aryltriazenes has been developed. With bis‐ (pinacolato)diboron as the borylation reagent, aryldiazonium tetrafluoroborate salts and aryltriazenes were transformed into the corresponding arylboronates in moderate to excellent yields under mild conditions. As a convenient and practical methodology, no additional ligands, base, or any other additives are required here.

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.