Xinxin Qi

Palladium‐Catalyzed One‐Pot Carbonylative Sonogashira Reaction Employing Formic acid as the CO Source

A convenient palladium-catalyzed carbonylative coupling of aryl iodides and terminal alkynes with formic acid as the CO precursor has been developed. A variety of alkynones were obtained in good yields in a one-pot manner for the first time.

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.

A Convenient Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source.

A practical palladium-catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas-free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids.

Palladium-catalyzed alkoxycarbonylation of aryl halides with phenols employing formic acid as the CO source

An efficient palladium-catalyzed alkoxycarbonylation of aryl halides with phenols has been developed. Various aryl benzoates have been isolated in good to excellent yields with formic acid as the CO source. The reaction proceeds smoothly under mild conditions and good functional group tolerance was observed.

A Convenient Palladium-Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid.

Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source.

Palladium‐Catalyzed Carbonylative Synthesis of Aryl Formates under Mild Conditions

Aryl formates have been extensively applied as CO sources in CO‐free carbonylation reactions. However, there are no catalytic synthetic procedures for their preparation. In this manuscript, we developed a convenient palladium‐catalyzed procedure for the synthesis of aryl formates. Good yields were achieved under mild reaction conditions with formic acid as the formyl source.

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.

A Convenient Palladium‐Catalyzed Carbonylative Synthesis of Benzofuran‐2(3 H)‐ones with Formic Acid as the CO Source

A general and convenient palladium-catalyzed carbonylation procedure for the synthesis of benzofuran-2(3 H)-ones from phenols and aldehydes has been developed. With formic acid as the CO source, a variety of benzofuran-2(3 H)-ones were obtained in moderate to good yields.

Selective palladium-catalyzed carbonylative synthesis of aurones with formic acid as the CO source

A general and practical strategy has been developed to prepare aurone derivatives. In the presence of the palladium catalyst, 2-iodophenol and terminal alkynes were reacted by using formic acid as the CO source with acetic anhydride as the additive. A variety of aurones were obtained in moderate to good yields. Notably, this is first report on carbonylative synthesis of aurones with formic acid as the CO source.

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.