Catalytic Lactonization of Unactivated Aryl C–H Bonds with CO<sub>2</sub>: Experimental and Computational Investigation

Song, Lei; Zhu, Lei; Zhang, Zhen; Ye, Jian‐Heng; Yan, Shusen; Han, Jie‐Lian; Yin, Zhu‐Bao; Lan, Yu; Yu, Da‐Gang

doi:10.1021/acs.orglett.8b01363

Cited by 69 publications

(23 citation statements)

References 91 publications

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“…Mechanistic investigations suggested that the palladacycle might be an active intermediate, which further reacted with CO 2 to generate the desired product. In another work, with benzylic alcohol as a directing group, the authors achieved [Pd(tfa) 2 ]‐catalyzed lactonization of unactivated aryl C−H bonds with CO 2 to afford phthalides (Scheme b). Remarkably, DFT calculations indicated that lactonization might involve insertion of two CO 2 into the O−Pd bond of the palladacycle, which is interesting and novel compared with previous reports.…”

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

confidence: 99%

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: 99%

C−H Bond Carboxylation with Carbon Dioxide

et al. 2019

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“…Recently, Yu and coworkers reported a lactonization reaction of unactivated aryl C−H bond with CO 2 . They proposed a mechanism based on the DFT calculation . Referring to their work and our preliminary mechanistic studies, a possible mechanism is proposed for this present catalytic reaction (Scheme ).…”

Section: Methodsmentioning

confidence: 80%

Palladium‐Catalyzed Inert C−H Bond Activation and Cyclocarbonylation of Isoquinolones with Carbon Dioxide Leading to Isoindolo[2,1‐b]isoquinoline‐5,7‐Diones

et al. 2019

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A palladium‐catalyzed inert C−H bond activation and cyclocarbonylation of isoquinolones leading to isoindolo[2,1‐b]isoquinoline‐5,7‐diones under 1 atm of carbon dioxide has been developed. This transformation features high regio‐ and chemo‐selectivity, step‐economy, and good functional group tolerance. Most of the corresponding products were obtained in moderate to good yields. It offers an alternative approach for the synthesis of useful diverse isoindolo[2,1‐b]isoquinoline‐5,7‐dione derivatives.

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“…Attempts to tease the intermediates out by mass spectrometry led to the observation of an interesting adduct involving two carbon dioxides, potentially implicating a unique nine-membered palladacycle (Scheme 6a) (a similar nine-membered metallacycle was recently supported computationally in another work). 42 Notably, under the optimized conditions, no α or β C-H activation of methyl groups (from a five-membered or six-membered palladacycle respectively) could be achieved, suggesting that if a tran-…”

Section: Mechanistic Questionsmentioning

confidence: 99%

Carbon Dioxide-Driven Palladium-Catalyzed C–H Activation of Amines: A Unified Approach for the Arylation of Aliphatic and Aromatic Primary and Secondary Amines

Kapoor

Chand-Thakuri²,

Maxwell³

et al. 2019

Synlett

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Amines are an important class of compounds in organic chemistry and serve as an important motif in various industries, including pharmaceuticals, agrochemicals, and biotechnology. Several methods have been developed for the C–H functionalization of amines using various directing groups, but functionalization of free amines remains a challenge. Here, we discuss our recently developed carbon dioxide driven highly site-selective γ-arylation of alkyl- and benzylic amines via a palladium-catalyzed C–H bond-activation process. By using carbon dioxide as an inexpensive, sustainable, and transient directing group, a wide variety of amines were arylated at either γ-sp3 or sp2 carbon–hydrogen bonds with high selectivity based on substrate and conditions. This newly developed strategy provides straightforward access to important scaffolds in organic and medicinal chemistry without the need for any expensive directing groups.1 Introduction2 C(sp3)–H Arylation of Aliphatic Amines3 C(sp2)–H Arylation of Benzylamines4 Mechanistic Questions5 Future Outlook

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Catalytic Lactonization of Unactivated Aryl C–H Bonds with CO₂: Experimental and Computational Investigation

Cited by 69 publications

References 91 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Palladium‐Catalyzed Inert C−H Bond Activation and Cyclocarbonylation of Isoquinolones with Carbon Dioxide Leading to Isoindolo[2,1‐b]isoquinoline‐5,7‐Diones

Carbon Dioxide-Driven Palladium-Catalyzed C–H Activation of Amines: A Unified Approach for the Arylation of Aliphatic and Aromatic Primary and Secondary Amines

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Catalytic Lactonization of Unactivated Aryl C–H Bonds with CO2: Experimental and Computational Investigation

Cited by 69 publications

References 91 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Palladium‐Catalyzed Inert C−H Bond Activation and Cyclocarbonylation of Isoquinolones with Carbon Dioxide Leading to Isoindolo[2,1‐b]isoquinoline‐5,7‐Diones

Carbon Dioxide-Driven Palladium-Catalyzed C–H Activation of Amines: A Unified Approach for the Arylation of Aliphatic and Aromatic Primary and Secondary Amines

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Catalytic Lactonization of Unactivated Aryl C–H Bonds with CO₂: Experimental and Computational Investigation