Palladium-Catalyzed Carbonylative Synthesis Research Articles

A general palladium-catalyzed carbonylative synthesis of α-CF3-substituted ketones and carboxylic acid derivatives

α-CF3-substituted carboxylic acid derivatives have drawn wide attention owing to their importance for both pharmaceutical and synthetic communities. However, methodologies for their construction are still very limited. Herein, we developed a general palladium-catalyzed carbonylative procedure for the synthesis of α-CF3-substituted ketones and carboxylic acid derivatives. With amines, phenols, alcohols, arylboronic acids, and even less-nucleophilic sulfonamides and amides as the reaction partners, the corresponding amides, esters, ketones and imides were obtained in good yields with excellent functional group tolerance. Furthermore, this protocol has also been applied to the late-stage modification of 25 densely functionalized pharmaceutical agents and natural products.

Palladium-catalyzed tandem carbonylative synthesis of indeno[1,2-b]indol-10(5H)-one scaffolds from 2-alkynylanilines

A novel palladium-catalyzed tandem cyclization and carbonylation of 2-alkynylanilines has been developed for the construction of indeno[1,2-b]indol-10(5H)-one scaffolds. By using formic acid as the CO source, this reaction proceeded smoothly to afford various indeno[1,2-b]indol-10(5H)-one derivatives in high yields. Notably, this protocol can be used in modifications of several bioactive molecules.

Palladium-Catalyzed Carbonylative Homocoupling of 2-Iodophenols for the Synthesis of Symmetrical Xanthones

AbstractHerein, we report the palladium-catalyzed carbonylative synthesis of symmetrical xanthones from functionalized 2-iodophenols in a one-pot manner. The protocol involves homocoupling of 2-iodophenols using Pd catalyst, Cs2CO3 as base, with gaseous CO as C1 building block. The simple, ligand- and additive-free strategy provides moderate to good yields of symmetrical xanthones. The reaction was also examined with the combination of 2-hydroxyphenyl boronic acid as another coupling partner. Additionally, this protocol was extended for the synthesis of aryl and alkyl salicylate derivatives by varying the reaction conditions.

Palladium-catalyzed carbonylative synthesis of carboxamide substituted 2-pynones from methyl enynoates and nitroarenes

A palladium-catalyzed carbonylative synthesis of carboxamide substituted 2-pynones from methyl enynoates and nitroarenes has been developed. With nitroarenes as the nitrogen sources, and Mo(CO)6 as both CO surrogate and reductant, a wide range of carboxamide substituted 2-pynones were obtained in moderate to high yields with quite high functional group compatibility. Moreover, the late-stage modifications of natural molecules was also achieved.

Palladium-Catalyzed Carbonylative Synthesis of Polycyclic 3,4-Dihydroquinolin-2(1H)-one Scaffolds Containing Perfluoroalkyl and Carbonyl Units.

A palladium-catalyzed one-pot two-step radical mediated carbonylative cyclization of 1,7-enynes with perfluoroalkyl iodides and Mo(CO)6 has been developed for the construction of polycyclic 3,4-dihydroquinolin-2(1H)-one scaffolds. This method realizes a facile synthesis of various polycyclic 3,4-dihydroquinolin-2(1H)-one derivatives containing perfluoroalkyl and carbonyl units in high yields. Moreover, modifications of several bioactive molecules were demonstrated using this protocol.

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 Synthesis of Amide-Containing Indolo[2,1-a]isoquinolines from Alkene-Tethered Indoles and Nitroarenes

In this new procedure, amide-containing indolo[2,1-a]isoquinoline scaffolds were prepared by palladium-catalyzed carbonylative cyclization of alkene-tethered indoles with nitroarenes. By using Mo(CO)6 as the CO source and reductant and nitroarenes as the nitrogen source, this reaction produced various amide-containing indolo[2,1-a]isoquinoline derivatives in good yields in general. Furthermore, the late-stage modifications of bioactive molecules using this protocol were demonstrated as well.

Additive-Controlled Divergent Synthesis of Indole and 4H-Benzo[d][1,3]oxazine Derivatives: Palladium-Catalyzed Carbonylative Cyclization of 2-Alkynylanilines and Benzyl Chlorides.

A palladium-catalyzed divergent carbonylative synthesis of indoles and 4H-benzo[d][1,3]oxazines from 2-alkynylanilines and benzyl chlorides with benzene-1,3,5-triyl triformate (TFBen) as the CO source has been developed. The reaction using AlCl3 as the additive produced various indoles in high yields, while a series of 4H-benzo[d][1,3]oxazines was achieved in moderate yields with AcOH as the additive.

Palladium-catalyzed carbonylative synthesis of indole-3-carboxamides from 2-ethynylanilines and nitroarenes

A facile and straightforward approach for the expedite construction of indole-3-carboxamide skeletons via a palladium-catalyzed carbonylative cyclization of 2-ethynylanilines with nitroarenes has been developed.

Palladium-Catalyzed Carbonylative Synthesis of Aryl Selenoesters Using Formic Acid as an Ex Situ CO Source.

A new catalytic protocol for the synthesis of selenoesters from aryl iodides and diaryl diselenides has been developed, where formic acid was employed as an efficient, low-cost, and safe substitute for toxic and gaseous CO. This protocol presents a high functional group tolerance, providing access to a large family of selenoesters in high yields (up to 97%) while operating under mild reaction conditions, and avoids the use of selenol which is difficult to manipulate, easily oxidizes, and has a bad odor. Additionally, this method can be efficiently extended to the synthesis of thioesters with moderate-to-excellent yields, by employing for the first time diorganyl disulfides as precursors.

Palladium-catalyzed carbonylative synthesis of 3-arylquinolin-2(1H)-ones from benzyl chlorides and o-nitrobenzaldehydes

• A general and straightforward palladium-catalyzed aminocarbonylation procedure of benzyl chlorides have been developed. • o- nitrobenzaldehydes have been used as stable nitrogen sources for the synthesis of 3-arylquinolin-2(1 H )-ones. • Mo(CO) 6 has been used both as CO precursor and reductant. A palladium-catalyzed carbonylative cyclization of benzyl chlorides with o- nitrobenzaldehydes has been developed for the synthesis of 3-arylquinolin-2(1 H )-ones. Mo(CO) 6 played a dual role as both a CO surrogate and a reductant in this carbonylative transformation.

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.

Palladium-catalyzed carbonylative cyclization of 2-alkynylanilines and aryl iodides to accessN-acyl indoles

A palladium-catalyzed carbonylative synthesis ofN-acyl indoles from 2-alkynylanilines and aryl iodides has been developed.

Palladium-catalyzed carbonylative synthesis of aryl esters from p-benzoquinones and aryl triflates.

A palladium-catalyzed dicarbonylation of p-benzoquinones with aryl triflates has been developed. Using Cr(CO)6 as the CO source, the reaction proceeds smoothly and efficiently to give a series of aryl esters in moderate to good yields (up to 90%).

Palladium-catalyzed carbonylative synthesis of 5-trifluoromethyl-1,2,4-triazoles from trifluoroacetimidohydrazides and aryl iodides

A new palladium-catalyzed three-component carbonylative procedure for the construction of 5-trifluoromethyl-1,2,4-triazoles from trifluoroacetimidohydrazides and aryl iodides has been developed. TFBen is applied as a safe and convenient solid CO surrogate here.

Palladium-catalyzed carbonylative synthesis and theoretical study of elongated tubular cavitands

Novel elongated resorcine[4]arene-based tubular cavitands were synthesized via various consecutive reaction steps including homogeneous catalytic carbonylation and cross-coupling processes. The effect of carbon monoxide pressure and different nucleophiles on the selectivity was examined and described. Molecular dynamics and DFT PBEPBE/6-31G(d,p) studies have been carried out for these new deepened cavitand structures to reveal the exact geometry, then QTAIM analysis at B3LYP-D3/def2-TZVP level was performed to shed light on the potential intramolecular weak interactions which have stabilizing effect on the cavitand structures.

Palladium-catalyzed carbonylative synthesis of acylstannanes from aryl iodides and hexamethyldistannane

In this communication, we describe a new method for the carbonylative synthesis of acylstannanes from aryl iodides and hexamethyldistannane. With Pd(PPh3)4 as the catalyst and toluene as the solvent at 60 °C under 10 bar CO for 16 h, the desired acylstannanes were obtained in good to excellent yields. In order to facilitate isolation and analysis, the obtained acylstannanes were transformed into the corresponding benzoic acids by simply stirring under air for 5 h.

Palladium-catalyzed carbonylative synthesis of α,β-unsaturated amides from aryl azides and alkenylaluminum reagent

In this work, an interesting procedure for the synthesis of α,β-unsaturated amides from aryl azides and alkenylaluminum reagent has been developed. With palladium as the catalyst and XPhos as the ligand under carbon monoxide pressure, the desired α,β-unsaturated amides were isolated in good to excellent yields with good functional group tolerance. Remarkably, this procedure also represents an example on addition of organometallic reagent to isocyanates for α,β-unsaturated amides synthesis.

Palladium-Catalyzed Carbonylative Synthesis of α-Branched Enones from Aryl Iodides and Arylallenes.

In this communication, an interesting carbonylation protocol for the preparation of α-branched enones has been established. Starting from readily available aryl iodides and allenes, with formic acid as the CO source and reductant, moderate to good yields of the desired enones were isolated. Although it is a carbonylation methodology, the use of a CO source can avoid the manipulation of CO gas directly. Notably, this procedure also presents the first example on carbonylative synthesis of α-branched enones.

Palladium-catalyzed three-component carbonylative synthesis of 2-(trifluoromethyl)quinazolin-4(3H)-ones from trifluoroacetimidoyl chlorides and amines

An efficient and practical approach for the synthesis of 2-(trifluoromethyl)quinazolin-4(3H)-ones through palladium-catalyzed three-component carbonylative reaction has been developed.