Article
Chemistry, Multidisciplinary
Ke Zhang, Xiao-Fei Liu, Wei-Min Ren, Xiao-Bing Lu, Wen-Zhen Zhang
Summary: Electrocarboxylation reaction is a powerful tool for the preparation of organic carboxylic acid by using CO2 as a carboxylative reagent. In some cases, CO2 also acts as a promoter to facilitate the desired reaction. Recent studies have focused on CO2-promoted electrocarboxylation reactions via CO2 center dot intermediate or transiently protective carboxylation of active intermediate with CO2.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Yang Li, Ying Wang, Yanru Zhang, Zhenpeng Wang, Junfeng Xiang, Juanjuan Han, Jun He, Longbo Zhang, Yanyan Wang, Qinglei Meng, Qingli Qian, Buxing Han
Summary: Here we present a strategy for synthesizing C-7 carboxylic acids by reacting glucose, CO2, and H2. The reaction was performed using Rh-(acac)-(CO)(2) as a catalyst and I-2 as a promoter in a binary solvent of acetic acid and water at 160 degrees C. This strategy also applies to other C(n) saccharides, yielding C(n+1) carboxylic acids with a maximum yield of 72% when glyceraldehyde was used. The reaction pathway was proposed based on several control experiments.
Article
Chemistry, Organic
Masanori Shigeno, Itsuki Tohara, Keita Sasaki, Kanako Nozawa-Kumada, Yoshinori Kondo
Summary: Interest in developing methods for direct CO2 fixation into readily available unfunctionalized C-H bonds in organic substances has recently surged. In this study, a combined Bronsted base was used to achieve the carboxylation of benzylic C-H bonds, resulting in the formation of various functional moieties.
Review
Chemistry, Organic
Zhengning Fan, Yaping Yi, Chanjuan Xi
Summary: This minireview summarizes the recent development in light-induced carboxylation of organic (pseudo)halides and analogues with CO2 via C-X (X=Br, Cl, O, N, etc.) bond cleavage.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Zhengning Fan, Shenhao Chen, Song Zou, Chanjuan Xi
Summary: The carboxylation reaction of allylic alcohols with carbon dioxide is achieved using photoredox/nickel dual catalysis, resulting in exclusively linear acids with good Z/E stereoselectivity. The use of Hantzsch ester as a reductant instead of stoichiometric metallic reductants allows the reaction to be carried out at room temperature with a blue LED light source. Mechanistic studies indicate that the presence of water in the catalytic system is crucial for the success of the reaction, which is likely to proceed through the oxidative addition of the in situ formed allylic hydrogen carbonate.
Article
Chemistry, Multidisciplinary
Shi Nan, Wang Hai-Bin, Gao Li, Zhang Jing-Yao, Guo Jian-Feng, Wang Fang, Abdolghaffar Ebadi
Summary: The vicinal difunctionalization of unsaturated carbon-carbon bonds with CO2 as a C1 building block is a powerful strategy for the synthesis of highly functionalized skeletons. This MiniReview summarizes recent advances in this research area, focusing on mechanistic features of reactions for catalyst improvement.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Chemistry, Multidisciplinary
La-Xia Wu, Fang-Jie Deng, Lin Wu, Huan Wang, Tai-jie Chen, Ye-Bin Guan, Jia-Xing Lu
Summary: A nickel-catalyzed regioselective electrocarboxylation of allylic halides with CO2 at atmospheric pressure has been developed, achieving moderate to good yields and high chain selectivity by adjusting reaction parameters. The reaction also shows tolerance to functional groups, and cyclic voltammetry was performed to propose a possible mechanism for the nickel-catalyzed CO2 allylation.
NEW JOURNAL OF CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Lucia Veltri, Roberta Amuso, Raffaella Mancuso, Bartolo Gabriele
Summary: This short review highlights the progress in utilizing palladium-catalyzed carbon dioxide for synthesizing valuable organic molecules. The review is organized based on the type of substrate used in the Pd-catalyzed carboxylation process, including olefinic substrates, acetylenic substrates, and other substrates such as aryl halides and triflates.
Article
Chemistry, Multidisciplinary
Wei Xu, Danjun Guo, Abdol Ghaffar Ebadi, Mohsen Toughani, Esmail Vessally
Summary: This article describes the achievements in the field of using organoboron compounds as reagents in the carboxylation reactions of organometallic compounds, and their applications in CO2 utilization, which is a rapidly growing research area.
JOURNAL OF CO2 UTILIZATION
(2021)
Review
Chemistry, Multidisciplinary
Sandeep Pimparkar, Aishwarya K. Dalvi, Adithyaraj Koodan, Siddhartha Maiti, Shaeel Ahmed Al-Thabaiti, Mohamed Mokhtar, Arnab Dutta, Yong Rok Lee, Debabrata Maiti
Summary: Carbon dioxide (CO2) is an exciting C1 source in synthetic organic chemistry, but its thermodynamic stability and kinetic inertness pose challenges for its direct fixation, which requires air-sensitive organometallic reagents. Researchers have successfully explored methods to incorporate CO2 into organic motifs, targeting different types of carbon bonds and developing various metal-based and metal-free catalytic strategies for CO2 fixation. This tutorial review aims to guide readers through the development of CO2 functionalization, addressing synthetic challenges, potential pitfalls, and future directions for CO2 utilization.
Article
Chemistry, Applied
Ke Jing, Ming-Kai Wei, Si-Shun Yan, Li-Li Liao, Ya-Nan Niu, Shu-Ping Luo, Bo Yu, Da-Gang Yu
Summary: The visible-light photoredox-catalyzed carboxylation of benzyl chlorides and bromides with CO2 has been reported. This carboxylation reaction utilizes inexpensive organic dyes as photocatalysts and amines as electron donors, without the need for sensitive organometallic reagents, transition metal catalysts, or metallic reductants. The reaction proceeds well on commercially available and inexpensive benzyl halides, yielding valuable aryl acetic acids, including several pharmaceutical molecules and drug precursors.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Lin Chen, Quan Qu, Chuan-Kun Ran, Wei Wang, Wei Zhang, Yi He, Li-Li Liao, Jian-Heng Ye, Da-Gang Yu
Summary: We report a novel visible-light photocatalytic carboxylation of C-N bonds in cyclic amines with CO2 via consecutive photo-induced electron transfer (ConPET). It is the first photocatalytic reductive ring-opening reaction of azetidines, pyrrolidines, and piperidines. This strategy enables the transformation of easily available cyclic amines into valuable amino acids in moderate-to-excellent yields. The method features mild and transition-metal-free conditions, high selectivity, good functional-group tolerance, facile scalability, and product derivations. Mechanistic studies suggest that ConPET plays a key role in generating highly reactive photocatalysts for the reductive activation of cyclic amines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Md. Saeedur Rahman, Ye Xu
Summary: Density functional theory calculations were used to study the activation and coupling reactions of CH4 and CO2 on metal surfaces. The results showed that the activation energy for C-H bond scission in CH4 was low on most metals except for the coinage metals. The coupling reaction between CH3 and CO2 was found to have higher activation energies on most metals. However, the formation of acetate was not feasible on monometallic surfaces.
Article
Chemistry, Multidisciplinary
H. Senboku
Summary: Over the past three decades, the focus has been on utilizing electrochemical methods to fix carbon dioxide and produce carboxylic acids through carbon-carbon bond forming reactions, known as electrochemical carboxylation. Various effective substrates have been identified, leading to the successful synthesis of a range of carboxylic acids, including pharmaceuticals and fluorinated analogues. Additionally, new reaction methods and technologies have been developed to advance the field of electrochemical carboxylation.
Article
Chemistry, Multidisciplinary
Ke Zhang, Bai-Hao Ren, Xiao-Fei Liu, Lin-Lin Wang, Min Zhang, Wei-Min Ren, Xiao-Bing Lu, Wen-Zhen Zhang
Summary: This paper reports a highly selective and direct electroreductive ring-opening carboxylation of epoxides with CO2 in an undivided cell, showing broad substrate scopes within styrene oxides and providing a practical and scalable access to important synthetic intermediate β-hydroxy acids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)