Pd-catalyzed carbonylation of aryl C–H bonds in benzamides with CO<sub>2</sub>

Song, Lei; Cao, Guang‐Mei; Zhou, Wen‐Jun; Ye, Jian‐Heng; Zhang, Zhen; Tian, Xing‐Yang; Li, Jing; Yu, Da‐Gang

doi:10.1039/c8qo00433a

Cited by 49 publications

(11 citation statements)

References 90 publications

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“…In 2018, Yu and co‐workers reported the first [Pd(tfa) 2 ]‐catalyzed (TFA=trifluoroacetate) benzamide‐directed carbonylation of unactivated aryl C−H bonds with atmospheric CO 2 to afford a series of phthalimides (Scheme a) . Mechanistic investigations suggested that the palladacycle might be an active intermediate, which further reacted with CO 2 to generate the desired product.…”

Section: Carboxylation Of C(sp2)−h Bonds With Co2mentioning

confidence: 96%

C−H Bond Carboxylation with Carbon Dioxide

et al. 2019

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Carbon dioxide is a nontoxic, renewable, and abundant C1 source, whereas C−H bond functionalization represents one of the most important approaches to the construction of carbon–carbon bonds and carbon–heteroatom bonds in an atom‐ and step‐economical manner. Combining the chemical transformation of CO2 with C−H bond functionalization is of great importance in the synthesis of carboxylic acids and their derivatives. The contents of this Review are organized according to the type of C−H bond involved in carboxylation. The primary types of C−H bonds are as follows: C(sp)−H bonds of terminal alkynes, C(sp2)−H bonds of (hetero)arenes, vinylic C(sp2)−H bonds, the ipso‐C(sp2)−H bonds of the diazo group, aldehyde C(sp2)−H bonds, α‐C(sp3)−H bonds of the carbonyl group, γ‐C(sp3)−H bonds of the carbonyl group, C(sp3)−H bonds adjacent to nitrogen atoms, C(sp3)−H bonds of o‐alkyl phenyl ketones, allylic C(sp3)−H bonds, C(sp3)−H bonds of methane, and C(sp3)−H bonds of halogenated aliphatic hydrocarbons. In addition, multicomponent reactions, tandem reactions, and key theoretical studies related to the carboxylation of C−H bonds are briefly summarized. Transition‐metal‐free, organocatalytic, electrochemical, and light‐driven methods are highlighted.

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Section: Carboxylation Of C(sp2)−h Bonds With Co2mentioning

confidence: 96%

C−H Bond Carboxylation with Carbon Dioxide

et al. 2019

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“…This type of reaction can be employed for utilizing low-value and nontoxic carboxylic acids as sustainable resources in C–C bond formation processes such as arylations or olefinations. , Regarding the utilization of CO 2 , various aromatic carboxylic acids are desirable target compounds, due to their wide application in pharmaceuticals and other high-value compounds. , There are plenty of examples using CO 2 as a carbon source in homogeneously catalyzed carboxylation reactions on preactivated arenes, such as organo-zinc or -boron − compounds or aryl (pseudo)halides. − Yet, to achieve high atomic efficiency, the direct catalytic carboxylation of non-preactivated arenes is very desirable to stay in line with the principles of green chemistry. In the last decade, among others, the groups of Hou, Nolan, and Iwasawa were able to realize catalytic direct carboxylation of arenes which still require strongly electron withdrawing substituents, − directing groups at the aromatic compound, − or addition of stoichiometric amounts of organometallic reagents. − Insertion of CO 2 into metal–aryl bonds is always a key step of these transformations.…”

Section: Introductionmentioning

confidence: 99%

Reversible Insertion of Carbon Dioxide at Phosphine Sulfonamido Pd^II–Aryl Complexes

et al. 2020

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Phosphine sulfonamido Pd(II) complexes bearing p-anisyl ([(P,N)Pd(4-OMe-C6H4)L]; L = C5H5N, 5-py; L = OS(CH3)2, 5-dmso) or carboxylato ([(P,N)Pd(OOCR)], 1-X: R = 4-OMe-C6H4, 1- p An; R = t Bu, 1-Piv; R = C6H5, 1-Ph) ligands were synthesized and their structures and dynamic behaviors were characterized. The compound 5-dmso can effectively be converted to 1- p An by migratory insertion of carbon dioxide into the Pd–aryl bond with precoordination of the CO2 molecule. Additionally, carboxylato-substituted compounds 1-X can serve as catalysts for protodecarboxylation reactions of bis-o-OMe-substituted carboxylic acids at room temperature without the need for an external proton source. Stoichiometric decarboxylative coupling of these acids with styrene selectively yields 1,1-diarylated olefins.

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“…In alternative protocols, CO was replaced by a more benign N , N ‐dimethyloxamic acid giving lower yields and using diethyl azodicarboxylate (DEAD) instead of CO led to the product resulting from ortho ‐C−H ethoxycarboxylation (R‐CO 2 Et) with the same anilide site‐selectivity . A reversed site‐selectivity with a palladium catalyst was reported using CO 2 in a poor yield . In this case, an intramolecular reaction cascade occurred leading to N ‐phenylphthalimide (Scheme ).…”

Section: C−c Bond‐forming Reactionsmentioning

confidence: 99%

Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides

Gramage‐Doria

2020

Chemistry A European J

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SelectiveC ÀHb ond functionalization catalyzed by metal complexes have completely revolutionized the wayi n which chemical synthesis is conceived nowadays. Typically, the reactivityo fat ransitionm etal catalyst is the key to control the site-, regio-and/or stereo-selectivity of aC ÀHb ond functionalization. Of particulari nterests are molecules that contain multiple CÀHb onds prone to undergo CÀHb ond activations with very similar bond dissociation energies at different positions. This is the case of benzanilides, relevant chemical motifs that are found in many useful fine chemicals, in which two CÀHs ites are present in chemically different aromatic fragments. In the last years, it has been found that depending on the metal catalyst and the reaction conditions, the amide motif might behave as ad irecting group towardst he metal-catalyzed CÀHb ond activation in the benzamide site or in the anilides ite. The impact and the consequences of such subtle control of site-selectivity are herein reviewed with important applicationsi ncarboncarbon and carbon-heteroatomb ond forming processes. The mechanisms unraveling these unique transformations are discussed in order to provide ab etter understanding for future developmentsi nt he field of site-selective CÀHb ond functionalization with transition metal catalysts.

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Pd-catalyzed carbonylation of aryl C–H bonds in benzamides with CO₂

Abstract: Herein, we report the first Pd-catalyzed carbonylation of unactivated aryl C–H bonds in benzamides under 1 atm of CO2 to directly afford important phthalimides.

Cited by 49 publications

References 90 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Reversible Insertion of Carbon Dioxide at Phosphine Sulfonamido Pd^II–Aryl Complexes

Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides

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Pd-catalyzed carbonylation of aryl C–H bonds in benzamides with CO2

Abstract: Herein, we report the first Pd-catalyzed carbonylation of unactivated aryl C–H bonds in benzamides under 1 atm of CO2 to directly afford important phthalimides.

Cited by 49 publications

References 90 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Reversible Insertion of Carbon Dioxide at Phosphine Sulfonamido PdII–Aryl Complexes

Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides

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Pd-catalyzed carbonylation of aryl C–H bonds in benzamides with CO₂

Reversible Insertion of Carbon Dioxide at Phosphine Sulfonamido Pd^II–Aryl Complexes