Palladium-catalyzed Carbonylative Reaction Research Articles

Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives.

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade reaction undergoes a sequence of oxidative addition, unsaturated bond migration, carbonyl insertion, and nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines and aliphatic amines could proceed smoothly in this transformation under one atm of CO.

Palladium-Catalyzed Iodine Assisted Carbonylation of Indoles with ClCF2CO2Na and Alcohols.

A palladium-catalyzed iodine-assisted carbonylation reaction of indoles with readily available ClCF2CO2Na and alcohols has been developed. This protocol provides a practical and efficient approach to highly regioselective indole-3-carboxylates via a preiodination strategy of indoles. Different from classic carbonylation using toxic and difficult-to-handle carbon monoxide, this operationally simple and scalable reaction employed difluorocarbene as the carbonyl surrogate.

Site-selective carbonylation of arenes via C(sp2)-H thianthrenation: Palladium-catalyzed direct access to α,β-unsaturated ketones

Herein, an efficient palladium-catalyzed carbonylative Heck reaction of aryl thianthrenium salts with carbon monoxide and alkenes has been developed. This protocol can greatly reduce the quantity of olefins used in the carbonylative Heck reaction. In addition, the reaction can also proceed when the coupling partner is a non-activated olefin which is not common in such carbonylative Heck reactions. Combined with C–H thianthrenation of aromatic hydrocarbons, this work provides an efficient method for the site-selective C–H carbonylative Heck reaction of aromatic hydrocarbons. It may serve as a significant late-stage carbonylation tool for the modification of complex molecules in the future.

Palladium-Catalyzed Carbonylation Reaction of Indole/Pyrrole Involving HCFO-1233zd (E).

3-Indole-3-one is a key intermediate in the synthesis of many drugs and plays an important role in synthetic chemistry and biochemistry. A new method for synthesizing trifluoromethylated 3-indoleketones by Pd(0)-catalyzed carbonylation was introduced. In the absence of additives, 1-chloro-3,3,3-trifluoropropyl (an inexpensive and environmentally friendly synthetic block of trifluoromethyl) reacts with indole and carbon monoxide to generate trifluoromethylindole ketones with good yields, regioselectivity, and chemical selectivity; furthermore, the products exhibit strong resistance to basic functional groups, such as alkynes, aldehydes, and esters. In addition to the conversion of indole compounds into corresponding products, pyrrole and heteroindole may be suitable for corresponding chemical transformations. This study provides a synthetic method for the further construction of trifluoromethylated 3-indole ketones.

Palladium-catalyzed desulfonylative carbonylation reaction of benylsulfonyl chlorides with anthranils for the synthesis of 3-arylquinoin-2(1H)-ones

A direct and efficient palladium-catalyzed desulfonylative carbonylation reaction for the synthesis of 3-arylquinoin-2(1H)-ones has been disclosed. The reaction proceeds with a rapid elimination of SO2 process by employing benzylsulfonyl chlorides as effective C(sp3) electrophiles, with anthranils as the N-source, a variety of 3-arylquinoin-2(1H)-ones were obtained in moderate to high yields. This protocol provides a good supplement for applying benzylsulfonyl chlorides as C(sp3) electrophiles in carbonylation reactions.

Palladium-catalyzed carbonylation of activated alkyl halides via radical intermediates

In this review, we summarize and discuss recent achievements in palladium-catalyzed carbonylative reactions of activated alkyl halides. Aliphatic carboxylic acid derivates were prepared effectively with various nucleophiles.

Palladium-Catalyzed Tandem Cyclization of Bromoalkynes, Anilines and CO: Access to 1,3-Substituted Maleimides.

A novel palladium-catalyzed three-component carbonylation reaction for the assembly of various 1,3-substituted maleimide derivatives from haloalkynes and simple anilines. The nucleophilic addition reaction of haloalkynes, anilines and CO, and insertion of carbonyl have been achieved sequentially in this reaction. The high chemo- and regioselectivities, as well as no need of expensive ligands or additives further illustrate the synthetic value of this approach.

Palladium-Catalyzed Carbonylative Synthesis of Diaryl Ketones from Arenes and Arylboronic Acids through C(sp2)-H Thianthrenation.

The development of mild methodology for converting inert C-H bonds to value-added molecules has been an attractive research topic during the last few decades as it offers efficient preparation. Meanwhile, diaryl ketones hold potent applications in antitumor drugs, the agrochemical industry, and synthetic chemistry. Herein, we report versatile palladium-catalyzed carbonylative cross-coupling reactions of aryl thianthrenium salts with arylboronic acids. Arenes were transformed site selectively via C(sp2)-H thianthrenation, and various desired diaryl ketones were produced in good to excellent yields.

Palladium-Catalyzed Carbonylative Hiyama-Denmark Reaction toward the Synthesis of Aryl Carbonyl-Containing Oxindoles.

A palladium-catalyzed domino Heck cyclization/carbonylative Hiyama-Denmark cross-coupling reaction between alkene-tethered aryl iodides and silylcarboxylic acids is presented. This reaction proceeds well without toxic carbon monoxide (CO) gas and has good functional group tolerance, providing an alternative access to carbonyl-containing oxindoles. In this transformation, silylcarboxylic acids play a dual role as a CO source and a nucleophile.

Synthesis of Spirocyclic and Bis-Indolinones via Palladium-Catalyzed Carbonylation Reactions

Key words palladium catalysis - chemodivergent carbonylation - isoindolinones

Enantioselective Double Carbonylation Enabled by High-Valent Palladium Catalysis.

Palladium-catalyzed carbonylation reactions are efficient methods for synthesizing valuable molecules. However, realizing a carbonylation with excellent yield and chemo-, regio-, and enantioselectivities by classical low-valent palladium catalysis is highly challenging. Herein, we describe an enantioselective carbonylation reaction using a high-valent palladium catalysis strategy and employing a chiral sulfoxide phosphine (SOP) ligand. This double aminocarbonylation reaction begins with the formation of a carbamoylpalladium(II) species, which undergoes enantioselective oxidative addition with a cyclic diaryliodonium salt to generate a palladium(IV) intermediate, followed by a second CO insertion and reductive elimination. The mechanism has been illustrated with experimental and computational studies.

Palladium-Catalyzed Chemodivergent Carbonylation of ortho-Bromoarylimine to Biisoindolinones and Spiroisoindolinones.

We herein report a palladium-catalyzed carbonylative cyclization reaction of ortho-bromoarylimines that allows for the chemodivergent synthesis of functionalized biisoindolinones and spirocyclic isoindolinones. Either product could be selectively obtained by switching the reaction temperatures and ligands, and the biisoindolinone products could be afforded facilely with catalyst loadings as low as 0.05 mol %. Further transformation of the biisoindolinone product is also described, which represents a novel and concise approach to the biisoindoline diamine ligand.

27 Years of Catalytic Carbonylative Coupling Reactions in Hungary (1994-2021).

Palladium-catalyzed carbonylation reactions, in the presence of nucleophiles, serve as very potent tools for the conversion of aryl and alkenyl halides or halide equivalents to carboxylic acid derivatives or to other carbonyl compounds. There are a vast number of applications for the synthesis of simple building blocks as well as for the functionalization of biologically important skeletons. This review covers the history of carbonylative coupling reactions in Hungary between the years 1994 and 2021.

Recent Developments on Palladium-Catalyzed Carbonylation Reactions in Renewable Solvents

Palladium-catalyzed carbonylation reaction has surfaced as a robust tool for insertion of the carbonyl group into organic molecules, and in the last decades enormous progress has been made. Nowadays, a plethora of methodologies is available to synthesize all kinds of carbonyl compounds. However, the focus has shifted during recent years to address rising concerns related to developing safe, cost-efficient, and more sustainable methodologies. The use of different carbon monoxide (CO) precursors/sources, avoiding handling of highly toxic and flammable gaseous carbon monoxide, and substituting nonrenewable solvents for those derived from renewable feedstock have contributed to aim these goals. In this review, we will discuss the advent of the application of renewable solvents to improve the sustainability and environmentally benign nature of Pd-catalyzed carbonylation reactions.

Pd-Catalyzed carbonylative lactonization of 2-halidearomatic aldehydes with H2O as a nucleophile.

A palladium-catalyzed carbonylative cyclization reaction of 2-halidebenzaldehydes with H2O is described, which provides a strategy for the synthesis of diversely substituted 3,3'-oxyphthalides. Notably, the obtained 3,3'-oxyphthalide could be easily transformed into 3-aryl and alkyl phthalides with excellent efficiency using organozinc reagents under mild reaction conditions.

Palladium-catalyzed cascade Heck-type thiocarbonylation for the synthesis of functionalized thioesters

A palladium-catalyzed cascade Heck-type cyclization and carbonylation reaction has been developed for the synthesis of functionalized thioesters.

Palladium-Catalyzed Enantioselective Intramolecular Heck Carbonylation Reactions: Asymmetric Synthesis of 2-Oxindole Ynones and Carboxylic Acids.

Herein, we report a Pd-catalyzed enantioselective domino Heck carbonylation reaction of o-iodoacrylanilides with terminal alkynes and water as the nucleophiles, affording a diversity of β-carbonylated 2-oxindole derivatives bearing a 3,3-disubstituted all-carbon quaternary stereocenter, in high yields (55-99 %) with good to excellent enantioselectivities (up to 99 % ee). The synthetic utilities of the protocol were demonstrated in the gram-scale synthesis of 2-oxindole-derived ynone 3 ea and carboxylic acid 4 a, as well as the facile synthesis of chiral 2-oxindoles with a pyrazole or isoxazole moiety.

Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

Nickel-Catalyzed Reductive Asymmetric Aryl-Acylation and Aryl-Carbamoylation of Unactivated Alkenes

Palladium-catalyzed carbonylative synthesis of quinazolines: Silane act as better nucleophile than amidine

Abstract A palladium-catalyzed reductive carbonylation reaction has been developed for the synthesis of quinazolines. With N-(2-iodophenyl)benzimidamide as starting materials, a series of quinazolines were obtained through the aromatic aldehyde intermediates in moderate to good yields with good functional group compatibilities. In this system, silane act as better nucleophile than amidine.

Synthesis of novel aromatic polyamides containing both sulfone linkages and cardo groups by a recyclable palladium-catalyzed carbonylation and condensation polymerization

A series of novel aromatic polyamides containing both sulfone linkages and cardo groups were synthesized via a heterogeneous palladium-catalyzed carbonylation and condensation reaction of aromatic diiodides bearing ether sulfone linkages, carbon monoxide, and aromatic diamines with cardo groups. Polycondensation reaction proceeded smoothly under 1 atm of CO at 120 °C in N,N-dimethylacetamide (DMAc) by using a bidentate phosphine ligand-modified magnetic nanoparticles-anchored palladium complex [2P-Fe3O4@SiO2-PdCl2] as a recyclable catalyst with 1,8-diazabicycle[5,4,0]-7-undecene (DBU) as a base, furnishing cardo poly(ether sulfone amide)s with inherent viscosities between 0.70 and 0.77 dL/g. The resulting polyamides could be readily dissolved in polar aprotic organic solvents and even dissolved in less polar pyridine and tetrahydrofuran at room temperature and could be easily converted into flexible, transparent, and tough films via casting from their solutions in DMAc. These polymers exhibited excellent thermal stability with the glass transition temperatures between 241 and 283 °C and the temperatures at 5% weight loss ranging from 438 to 475 °C in an atmosphere of nitrogen. The polyamide films displayed good mechanical behavior with tensile strengths of 78.8–84.4 MPa, tensile moduli of 2.08–2.57 GPa, and elongations at breakage of 10.2–12.5%, and optically high transparency with cut-off wavelengths in the range of 338–368 nm.