Article
Chemistry, Multidisciplinary
Qian Zhang, Jing Hou, Yan Huang, Le-wu Zhan, Bin-dong Li
Summary: A novel method for the synthesis of ureas and formamides using visible-light-induced Ph3P-promoted reactions is reported. Ureas can be directly synthesized at ambient temperature and pressure without external additions. Formamides can be produced by using triisopropylsilanethiol as the hydrogen source.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhi-Qiang Wang, Cheng-Hua Deng, Xiao Liu, Wen-Min Wang
Summary: In this study, a green-synthesis produced aluminum-based metal-organic framework (Al-MOF) material CAU-10pydc was used as a catalyst for CO2 formylation reaction. The results showed that CAU-10pydc could effectively catalyze the reaction of CO2 and N-methylaniline to N-methyl-N-phenylformamide under mild conditions. CAU-10pydc maintained its efficient catalytic performance after cyclic catalysis and exhibited stability. The universality of this catalyst was demonstrated through reactions with nine substrates. This work represents the first example of a highly effective Al-MOF catalyzing CO2 formylation reaction under green conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhaozhuo Yu, Zhengyi Li, Lilong Zhang, Kaixun Zhu, Hongguo Wu, Hu Li, Song Yang
Summary: Chemocatalytic upgrading of CO2 to valuable chemicals and biofuels has drawn significant attention, with N-formylation of CO2 with an amine playing a crucial role in constructing N-containing linear and cyclic skeletons. A stable N-heterocyclic carbene-carboxyl adduct (NHC-CO2) was developed as a recyclable zwitterionic catalyst for efficient CO2 reductive upgrading, achieving remarkable yields of up to 98%. The introduced substituent on NHC-CO2 was found to impact its thermostability and nucleophilicity, directly influencing catalytic activity. Additionally, NHC-CO2 demonstrated the ability to supply CO2 through in situ decarboxylation at specific temperatures.
Article
Chemistry, Physical
Qinggang Ren, Yaju Chen, Yongjian Qiu, Leiming Tao, Hongbing Ji
Summary: Porous hypercrosslinked polymer was modified with quaternary ammonium bromide before and after synthesis to create a highly efficient CO2 conversion catalyst PiP@QA, showing improved catalytic performance and selective adsorption capabilities. The catalyst exhibited excellent reusability and potential for industrial application in chemical recycling of CO2 into valuable products.
Article
Chemistry, Organic
Koichi Nakaoka, Chao Guo, Yuta Saiki, Shin Furukawa, Tadashi Ema
Summary: In this study, TBAA and Cu(OAc)(2) were used as a binary catalytic system for the solvent-free N-formylation of amines with CO2 and PhSiH3. This catalysis not only synthesized enamines, aldehydes, and nitriles, but also formed C-H and C-N bonds, achieving a one-pot synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shang-Yuan Lu, Wei Chen, Lang-Qi Wen, Hui Zhou
Summary: The carboxylative cyclization of propargylic alcohols with CO2 was successfully achieved using pyridinylidenaminophosphines (PYA-Ps) as organocatalysts for the first time. The reaction showed excellent chemo- and stereo-selectivity, leading to moderate to good yields of alpha-methylene cyclic carbonates. Density functional theory (DFT) calculations revealed that the catalytic reaction proceeded through a PYA-Ps-mediated basic ionic pair mechanism, with intramolecular cyclization as the rate-determining step. The catalytic versatility of PYA-Ps was further explored for the transformation of CO2 to functionalized cyclic carbonates and N-formylated amines.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Guoqing Wang, Miao Jiang, Guangjun Ji, Zhao Sun, Lei Ma, Cunyao Li, Hong Du, Li Yan, Yunjie Ding
Summary: A highly efficient heterogeneous catalyst Pd@POPs was developed for the N-formylation reaction of amine and CO2 under mild conditions. The catalyst exhibited high BET surface areas and uniform dispersion of Pd active sites, showing excellent activity and stability for the reaction.
Article
Energy & Fuels
Bo Liu, Tong Duan, Zhenjiang Li, Weizhou Huang, Jinlan Li, Tianyu Zhu, Canliang Ma, Jie Sun, Kai Guo
Summary: The metal-and halide-free catalyst DABCO center dot HSac, consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO) and saccharin (HSac), effectively catalyzes the cycloaddition of CO2 into epoxides. The catalytic cycle involves the nucleophilic attack of the saccharinate anion on the methylene carbon of the epoxide ring, while the onium cation DABCO-H+ activates the epoxide. The use of non-halide anions as nucleophiles in halide-free catalyst design expands the possibilities for catalyst discovery.
Article
Chemistry, Applied
Janna V. Veselovskaya, Vladimir S. Derevschikov, Anton S. Shalygin, Dmitry A. Yatsenko
Summary: By impregnating porous zirconia aerogels with K2CO3, a series of composite materials were prepared, with the composite sorbent containing 23% K2CO3 demonstrating the highest CO2 absorption capacity. The study suggests that some of the K2CO3 loaded into zirconia mesopores do not actively participate in CO2 absorption and desorption processes.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Physical
Zecheng Ye, Jinzhu Chen
Summary: This study demonstrates the development of metal-organic frameworks (MOFs) with inner salt of 3-(pyridinylium)-1-propanesulfonate (PS) as catalysts (PS/MOFs) for the reductive functionalization of carbon dioxide (CO2) to benzimidazoles and N-formamides. The PS/MOFs show efficient catalytic activity for the synthesis of benzimidazoles and N-formamides through reductive cyclization. The research highlights the potential of MOF-based catalysts for organocatalytic transformation of CO2 into high value-added chemicals.
Article
Chemistry, Physical
Ruxu Yao, Youjie Li, Jiahuan Wang, Jinzhu Chen, Yisheng Xu
Summary: This study presents the crown ether-catalyzed reductive functionalization of CO2, leading to the formation of various N-containing benzoheterocyclics and N-formamides. The electron-donating ability of the investigated crown ethers positively correlates with their catalytic activity in CO2 reduction. This work demonstrates the significance of crown ethers as novel organocatalysts for CO2 reduction.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Subir Maji, Arpan Das, Swadhin K. Mandal
Summary: A new catalyst was introduced for the reductive functionalization of CO2 leading to consecutive double N-methylation of primary amines. The catalyst showed high efficiency in methylating a wide range of secondary and primary amines under mild conditions. Detailed mechanistic cycle was proposed through a series of control reactions and structural studies.
Article
Chemistry, Physical
Masoumeh Karimi Alavijeh, Mostafa M. Amini, Behrouz Notash, Gholamhossein Mohammadnezhad
Summary: A new 3D potassium coordination polymer and its sulfono-tricarboxylic ligand were successfully synthesized and characterized in this study. The catalytic activities of the ligand in the CO2 cycloaddition reaction were investigated, showing efficient performance possibly due to the synergetic effect among the functional groups.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Applied
Fan Yang, Yuta Saiki, Koichi Nakaoka, Tadashi Ema
Summary: This study reported the solvent-free N-formylation reaction catalyzed by Cu(OAc)(2), which used CO2 and phenylsilane to react with 2-(methylamino)pyridine and produced N-methyl-N-(2-pyridyl)formamide. The improved solubility of copper ion and enhanced nucleophilicity of acetate ion played positive roles in the activation of phenylsilane.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zhenzhen Zhou, Xiao Liu, Jian-Gong Ma, Peng Cheng
Summary: Environmental problem caused by carbon emission has attracted widespread attention. This study developed a new dual-active site catalyst for converting CO2 into formamides, which has the advantages of high efficiency, low cost, and reusability. It provides a reliable approach to unify the advantages of homogeneous and heterogeneous catalysts, and has significant implications for synthetic chemistry and environmental protection.
Article
Chemistry, Organic
Manjunath S. Lokolkar, Pravin A. Mane, Sandip Dey, Bhalchandra M. Bhanage
Summary: An effective method for synthesizing 2-substituted indoles through addition/reductive cyclization in a one-pot tandem reaction has been presented. This method tolerates a wide range of functional groups and provides moderate to good yields. The gram-scale synthesis of 2-substituted indole has also been demonstrated. This protocol offers an alternative route for the synthesis of 2-substituted indoles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Manjunath S. Lokolkar, Manoj K. Pal, Sandip Dey, Bhalchandra M. Bhanage
Summary: In this study, a new palladium complex was synthesized and used as a catalyst for the synthesis of oxygen-containing heterocyclic flavones. The synthesized complex was characterized and found to remain active even at low loading.
Article
Chemistry, Organic
Tejas A. Gokhale, Sanjivani C. Gulhane, Bhalchandra M. Bhanage
Summary: This study explores the utilization of bio-derived feedstocks in the catalyst-free oxidative synthesis of N-formamides. The results reveal that 1,3-dihydroxyacetone and glyoxal have the best carbon efficiency and can be used to synthesize a library of N-formamides. The methodology has demonstrated high yields in both laboratory and pilot scale.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Vijay P. Mahajan, Yuvraj A. A. Kolekar, Bhalchandra M. M. Bhanage
Summary: This study presents a magnetically separable nickel catalyst supported on Fe3O4 for phenoxy carbonylation reactions to synthesize aryl esters. The use of o-chlorophenyl formate as a CO source and phenol as a coupling partner, along with the inexpensive nickel catalyst, are the main advantages of this method. The Ni/Fe3O4 catalyst showed excellent magnetic separability due to the superparamagnetic nature of Fe3O4 and could be reused for up to eight cycles with minimal drops in yield. The protocol demonstrated tolerance towards various functionalities of aryl iodides and provided moderate to good yields of the corresponding esters. The prepared Ni/Fe3O4 nanoparticles were characterized using analytical techniques such as FESEM, EDS, TEM, XRD, ICP-OES, and XPS.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Tejas A. Gokhale, Tejashri J. Sarda, B. Bhalchandra M. Bhanage
Summary: This study reports on the sunlight driven rapid photodegradation of Crystal Violet using Magnesium doped Zinc oxide nanostructures. Among them, 5% Mg-ZnO showed exceptional photocatalytic performance with the highest kinetic rate constant. Under optimized conditions, 30 mg of 5% Mg-ZnO exhibited >85% photodegradation efficiency of 10 ppm of Crystal Violet in a short period of time.
MATERIALS CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yuvraj A. Kolekar, Vitthal B. Saptal, Bhalchandra M. Bhanage
Summary: This study successfully developed a catalyst with controllable activity and selectivity by combining mesoporous silica and N-rich melamine dendron through covalent grafting. The catalyst exhibited excellent catalytic activity for the oxidative carbonylative self-coupling reaction using N-formyl saccharin as a sustainable solid CO source and Cu as a co-catalyst.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Priyanka Jawale, Bhalchandra M. Bhanage
Summary: In this study, the synthesis of decanoate esters using immobilized lipase in deep eutectic solvent was investigated, and a suitable kinetic model was proposed. The best combination of DES and lipase for synthesizing propyl decanoate was found to be Gly:ChCl and Cal B, respectively. Response surface methodology was used to optimize reaction variables, and the activation energy was determined to be 14.59 kcal/mol. The study also showed that biocatalysts could be recycled for up to four cycles, and the reaction mechanism followed the Ping Pong Bi Bi mechanism. Molecular docking confirmed the acylation of the active site serine residue and strong hydrogen bonding between the substrate and active site.
JOURNAL OF THE INDIAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Satish M. Chauhan, Bhalchandra M. Bhanage
Summary: In this study, a catalyst-free synthesis method for quinazolinones using formic acid as a C1 source in the presence of triethylamine was developed. This simple and efficient approach provides a promising alternative to conventional routes and offers a sustainable solution for synthesizing quinazolinone derivatives.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Kasturi U. Nabar, Bhalchandra M. Bhanage, Sudam G. Dawande
Summary: An efficient, inexpensive, and environment-friendly method using copper sulfate as a catalyst and water as a green solvent has been developed for the N-arylation of amines with 1,3-cyclohexadione-derived aryliodonium ylides. Aromatic primary amines substituted with electron-donating or electron-withdrawing groups reacted smoothly, yielding diarylamines with good to excellent yields. Secondary amines also underwent N-arylation to give tertiary amines with moderate yields.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Vijay P. Mahajan, Yuvraj A. Kolekar, Bhalchandra M. Bhanage
Summary: This work presents a novel method for the synthesis of diaryl ketones through carbonylative homo-coupling reactions using a nickel catalyst supported on Al2O3. A heterogeneous Ni/Al2O3 catalyst was prepared and employed for the reaction of aryl iodides under carbon monoxide gas-free conditions. Good to excellent yields of symmetrical diaryl ketones were obtained using Co-2(CO)(8) as a carbon monoxide source. The catalyst demonstrated high stability with no significant loss of activity after five consecutive cycles.
Article
Chemistry, Physical
Tejas A. Gokhale, Prafull A. Jagtap, Bhalchandra M. Bhanage
Summary: This work presents a synthetic protocol for the synthesis of N-formamides using iron-based catalysis with magnetic Fe powder as the catalyst, achieving high yields and catalyst reusability.
Article
Chemistry, Multidisciplinary
Yuvraj A. A. Kolekar, Bhalchandra M. M. Bhanage
Summary: An efficient Pd/Cu-catalyzed self-carbonylation of arylhydrazines with CO and molecular oxygen has been developed, resulting in the synthesis of symmetrical biaryl ketones through C-N bond activation. The use of arylhydrazine hydrochlorides as green arylating agents allows for the release of nitrogen and water as byproducts. This protocol successfully suppresses the formation of aryl iodides and homo-coupled azobenzenes, even under favorable conditions, and allows for the synthesis of a library of symmetrical biaryl ketones with various functional groups in good yields under mild conditions.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Prafull A. Jagtap, Manjunath S. Lokolkar, Bhalchandra M. Bhanage
Summary: A simple, cost-effective, and straightforward method for the synthesis of 2,3-disubstituted indole scaffolds was developed. The reaction involves copper-mediated tandem hydroamination followed by C-H annulation of unprotected anilines with internal alkynes. The reaction proceeds well with Cu(OAc)(2)& BULL;H2O and trifluoroacetic acid (TFA), providing various substituted indole derivatives in moderate to good yields. The process is compatible with primary and secondary anilines as well as aromatic/aliphatic alkynes. High-purity copper nanoparticles can be recovered after the reaction, demonstrating the cost-effectiveness and environmentally benign nature of the protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Bhalchandra M. Bhanage
JOURNAL OF THE INDIAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Manjunath S. Lokolkar, Bhalchandra M. Bhanage
Summary: In this study, a palladium-catalyzed carbonylative synthesis method was developed for the one-pot synthesis of symmetrical xanthones. The protocol is simple, ligand- and additive-free, and provides moderate to good yields of the target compounds. It can also be extended for the synthesis of related derivatives.