Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jordan L. S. Zackasee, Samir Al Zubaydi, Blaise L. Truesdell, Christo S. Sevov
Summary: Mediator-assisted electrocatalysis is a general strategy to enhance the electroreductive cross-electrophile coupling (eXEC) reactions. Addition of a redox-matched mediator enables the catalyst-mediator systems to generate products in near-quantitative yield. This study also identifies a library of catalyst-mediator systems that can couple a wide range of substrate classes in high yields.
Article
Chemistry, Multidisciplinary
Lingxiang Lu, Yi Wang, Wendy Zhang, Wen Zhang, Kimberly A. See, Song Lin
Summary: The cross-electrophile dialkylation of alkenes allows for regioselective dialkylation of alkenes without the use of transition-metal catalysts, leading to the formation of two C-(sp(3))-C-(sp(3)) bonds. This method provides a modular and efficient approach to building structural complexity in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
David J. Charboneau, Haotian Huang, Emily L. Barth, Cameron C. Germe, Nilay Hazari, Brandon Q. Mercado, Mycah R. Uehling, Susan L. Zultanski
Summary: A series of new tunable homogeneous organic reductants based on a tetraaminoethylene scaffold have been synthesized, which exhibit enhanced air stability and solid state properties at room temperature. These reductants show significantly milder reduction potential than conventional reductants, allowing for controlled alkyl radical generation in Ni-catalyzed XEC reactions. The new reductants are expected to replace current homogeneous reductants due to their stability and lead to the development of novel synthetic methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Bincy Chindan, Anagha Syam, Hariharan Mahendran, Ramesh Rasappan
Summary: In this study, a method for synthesizing α-vinyltrialkoxysilanes via cross-electrophile C(sp(2))-C(sp(2)) coupling was reported. The method demonstrates high compatibility with functional groups under milder reaction conditions.
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Wei Shu
Summary: We report a reaction mode for the enantioselective construction of alkyl-alkyl bond to access saturated stereogenic carbon centers by asymmetric reductive cross-coupling between different alkyl electrophiles in good yields with great levels of enantioselectivity. This reaction mode uses only alkyl electrophiles for enantioselective C-sp3-C-sp3 bond-formation, rendering reductive alkyl-alkyl cross-coupling as an alternative to traditional alkyl-alkyl cross-coupling reactions between alkyl nucleophiles and alkyl electrophiles to access saturated stereogenic carbon centers without the use of organometallic reagents. The reaction displays a broad scope for two alkyl electrophiles with good functional group tolerance. Mechanistic studies reveal that the reaction undergoes a single electron transfer that enabled the reductive coupling pathway to form the alkyl-alkyl bond.
Article
Chemistry, Organic
Alexander J. Rago, Aristidis Vasilopoulos, Amanda W. Dombrowski, Ying Wang
Summary: In this study, a series of novel Di(2-picolyl)amines (DPAs) ligands were successfully synthesized using a facile method, and several of these ligands were found to be applicable for C(sp2)-C(sp3) cross-electrophile coupling.
Article
Chemistry, Organic
Xiaochun He, Jiangjun Liu, Gang Chen, Baojian Xiong, Xue Xiao, Lei Chen, Xuemei Zhang, Lin Dong, Xuelei Ma, Zhong Lian
Summary: A nickel-catalyzed cross-electrophile coupling of allylic acetates and gem-difluorovinyl tosylate has been developed. This reaction enables the synthesis of allylic gem-difluoroolefins via C(sp(3))-C(sp(2)) cross-electrophile coupling and proceeds under mild reaction conditions, providing a variety of allylic gem-difluorovinyl arenes in moderate to good yields. Mechanistic studies reveal the involvement of two different Ni(0)/Ni(II) catalytic cycles.
Review
Chemistry, Multidisciplinary
Yan-Long Zheng, Stephen G. Newman
Summary: This article discusses two common families of chemical reactions - cross-coupling reactions and pi bond addition reactions - and the significant overlap between them. Recent advancements in catalysis have revealed the role of compounds such as esters, aldehydes, and alcohols in nickel- and palladium-catalyzed reactions, offering promising alternatives for the preparation of amides, ketones, substituted alcohols, alkanes, and more. The focus is on the key mechanistic steps that allow these non-traditional substrates to be incorporated into cross-coupling-like catalytic cycles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Wen Zhang, Lingxiang Lu, Wendy Zhang, Yi Wang, Skyler D. Ware, Jose Mondragon, Jonas Rein, Neil Strotman, Dan Lehnherr, Kimberly A. See, Song Lin
Summary: Recent research in medicinal chemistry has found a correlation between an increase in sp(3) carbons in drug candidates and their improved success rate in clinical trials. This study focuses on the development of robust and selective methods for constructing carbon(sp(3))-carbon(sp(3)) bonds. By using electrochemistry, the researchers achieve the selective activation of alkyl halides based on their electronic and steric properties, allowing for high selectivity in carbon(sp(3))-carbon(sp(3)) cross-electrophile coupling. This new protocol shows improved chemoselectivity and does not require a transition metal catalyst.
Article
Chemistry, Organic
Andrew C. Jones, William I. Nicholson, Jamie A. Leitch, Duncan L. Browne
Summary: The nickel-catalyzed cross-electrophile coupling of aryl halides and alkyl halides enabled by ball-milling is efficient and green, achieving reductive C-C bond formation under a mechanochemical manifold. The mechanical action provided by ball milling allows for the use of a variety of zinc sources to turnover the nickel catalytic cycle, resulting in the synthesis of 28 cross-electrophile coupled products.
Article
Chemistry, Multidisciplinary
Xiang Liu, Cai-Yu He, Hao-Nan Yin, Chengping Miao, Xue-Qiang Chu, Weidong Rao, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A nickel-catalyzed cross-electrophile coupling of triazine esters with aryl bromides in the presence of magnesium and lithium chloride has been developed. The reactions proceed efficiently at room temperature through C-O bond activation, providing a variety of diaryl ketones in moderate to good yields with wide functional group tolerance.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Linlin Ding, Yue Zhao, Hongjian Lu, Zhuangzhi Shi, Minyan Wang
Summary: For the first time, a catalytic enantioselective propargyl-aryl cross-coupling between two electrophiles was achieved in a stereoconvergent manner. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Elizabeth R. Jarvo, Amberly B. Sanford
Summary: This article discusses the research conducted in the lab on the activation of alcohol derivatives in cross-coupling and cross-electrophile coupling reactions. The developed methods have enabled the use of secondary alcohols to produce tertiary stereogenic centers, which have been applied in the synthesis of pharmaceutically relevant compounds and substructures. The lab first focuses on the synthesis of bioactive compounds through stereospecific Kumada cross-coupling reactions and then discusses the development of a stereoselective cross-electrophile coupling reaction to synthesize cyclopropanes.
Article
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Loic R. E. Pantaine, David C. Blakemore, Ian B. Moses, Neal W. Sach, Andre Shavnya, Michael C. Willis
Summary: Heteroaromatic sulfinates are effective nucleophilic reagents in Pd-0-catalyzed cross-coupling reactions with aryl halides. Base-activated, latent sulfinate reagents, such as beta-nitrile and beta-ester sulfones, have been introduced to address challenges in purifying and solubilizing metal sulfinate salts, as well as their tolerance to multi-step transformations. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration and amenable to scale-up processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fariba Golpayegani, Zohreh Mirjafary, Hamid Saeidian, Javad Mokhtari
Summary: This study investigated ketene derivatives with cyclopropene and methylenecyclopropene substituents as powerful carbon superbases using theoretical calculations, revealing that the protonation of these compounds can lead to new neutral organic bases with high proton affinities. The basicity of the designed ketenes was enhanced by substituting electron-releasing groups on the molecular framework, and aromaticity indices like nucleus-independent chemical shift and harmonic oscillator model were utilized to explain the basicity of ketenes.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Masomeh Mahmoudi, Hamid Saeidian, Zohreh Mirjafary, Javad Mokhtari
Summary: In this study, a memantine release system based on polycaprolactone nanocapsules (MEM@PCL) was prepared for the first time, with an encapsulation efficiency of 80% as measured by high-performance liquid chromatography analysis. Physicochemical stability studies over 40 days demonstrated that the nanocapsules remained stable in solution without aggregation.
JOURNAL OF POROUS MATERIALS
(2021)
Article
Chemistry, Applied
Farideh Godarzbod, Zohreh Mirjafary, Hamid Saeidian, Morteza Rouhani
Summary: A new nanocatalyst Fe3O4@SiO2@IDA-Cu was prepared by the sol-gel method for the synthesis of 1,4-disubstituted-1,2,3-triazole derivatives. The catalyst exhibited spherical morphology, excellent yields, and environmentally friendly synthesis, and could be easily recovered and reused multiple times without significant loss of activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hossein Paghandeh, Maryam Khalili Foumeshi, Hamid Saeidian
Summary: A novel series of beta-hydroxy-1,4-disubstituted-1,2,3-triazole-based benzodiazepinedione derivatives were synthesized through a regioselective cascade reaction, showing high yields and ease of operation. The use of water as a green solvent and the avoidance of handling organic azides offer environmental advantages in this method. Additionally, DFT calculations were performed to characterize the structure and electronic properties, showing alignment with experimental data.
STRUCTURAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Mahdieh Mohammad Karbasi, Zohreh Mirjafary, Hamid Saeidian, Javad Mokhtari
Summary: Novel 1,2,3-triazole-dithiocarbamate hybrids were synthesized in moderate to good yields using a green solvent system, and their structures were characterized by various techniques. DFT analysis was used to study some properties of the products, with the calculated data in close agreement with experimental data.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Organic
Hamid Saeidian, Hadi Malekian, Esmail Vessally
Summary: The study computationally investigated the hydride affinity of 20 allene and heteroallene derivatives containing unsaturated rings such as cyclopentadiene. The interaction of molecules with electron-withdrawing groups on the CP ring and hydride ion was found to be highly desirable, with aromaticity of the CP anion playing a key role in increasing and stabilizing the hydride affinity. The study also examined the protonation of designated allenes containing different ring structures, as well as performing charge distribution analysis using electrostatic potential maps.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Baharak Farzin, Hamid Saeidian, Zohreh Mirjafary, Javad Mokhtari Aliabad
Summary: Density functional theory (DFT) calculations were performed on a new set of organic Bronsted acids based on the 9H-fluorene scaffold, determining their optimal structures, acidity, and tautomerization processes. The acidity of the designed compounds was calculated using computational methods, with some compounds found to be superacids. Aromaticity indices and charge distribution analysis were also conducted for the designed compounds and their conjugate bases.
STRUCTURAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zohreh Esmaeeli, Mohammad Reza Khodabakhshi, Zohreh Mirjafary, Hamid Saeidian
Summary: In this study, 12 new dispiroheterocycles containing aurone scaffold were successfully synthesized with high yields through a three-component 1,3-dipolar cycloaddition reaction. The comparison between experimental and theoretical results shed light on the regioselectivity of the reaction.
STRUCTURAL CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Ewa D. Raczynska, Jean-Francois Gal, Pierre-Charles Maria, Hamid Saeidian
Summary: This study investigates the gas-phase basicity enhancement of nitriles through theoretical methods and identifies the push-pull effect of cyclopropenimine and methylenecyclopropene, as well as their derivatives. The protonation of the cyano group is found to be favored, and strong electron donor X substituents exhibit similar push-pull effects in the two pi-systems. The calculated proton affinities enrich the gas-phase basicity scale of nitriles to around 1000 kJ mol(-1).
Article
Engineering, Environmental
Masomeh Mahmoudi, Hamid Saeidian, Zohreh Mirjafary, Javad Mokhtari
Summary: A 7-MEOTA delivery system based on polycaprolactone nanocapsules was prepared and investigated, showing stable physico-chemical properties with controlled drug release. The drug amount loaded in nanocapsules was estimated at 65%, with spherical nanoparticles free of aggregation. In vitro release experiments indicated controlled release of 7-MEOTA from the nanocapsules, following Fick's law of diffusion.
JOURNAL OF POLYMERS AND THE ENVIRONMENT
(2022)
Article
Biochemical Research Methods
Seyed Esmaeil Hosseini, Sajjad Mousavi Faraz, Mohammad Taghi Naseri, Davood Ashrafi, Hamid Saeidian
Summary: This study prepared a new category of selenophosphorus compounds using microsynthetic protocols and investigated their fragmentation pathways using mass spectrometry. The results revealed interesting fragmentation pathways, highlighting the importance of this research in identifying CWC-related chemicals during on-site inspection and off-site analysis.
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
(2022)
Article
Physics, Atomic, Molecular & Chemical
Masomeh Eskandari, Sajjad Mousavi Faraz, Seyed Esmaeil Hosseini, Shahram Moradi, Hamid Saeidian
Summary: The mass spectral data of a new group of Novichok organophosphorus nerve agent derivatives were studied, and the fragmentation pathways were proposed and confirmed using deuterated analogs and DFT calculations. Several new fragmentations and rearrangements were observed. The findings from this study are helpful in detecting CWC-related chemicals during on-site and/or off-site inspection.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Chemistry, Multidisciplinary
Arjang Jalezadeh, Zohreh Mirjafary, Morteza Rouhani, Hamid Saeidian
Summary: Calycopetrin and xanthomicrol, extracted from plants, are polymethoxylated flavones with extraordinary biological properties. Their structural, electronic, and spectral data were obtained using computational methods and their antioxidant properties and reactivity with oxygen radicals were evaluated.
STRUCTURAL CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Ewa D. Raczynska, Jean-Francois Gal, Pierre-Charles Maria, Ghulam Sakhi Sakhawat, Mohammad Qasem Fahim, Hamid Saeidian
Summary: This work investigates the gas-phase basicity of two series of nitriles and analyzes their isomeric phenomena and substituent effects. By calculating the microscopic and macroscopic gas-phase basicity parameters, the alkalinity properties are predicted.
Article
Biochemistry & Molecular Biology
Zohreh Mirjafary, Mahdieh Mohammad Karbasi, Parsa Hesamzadeh, Hamid Reza Shaker, Asghar Amiri, Hamid Saeidian
Summary: A series of 1,2,3-triazole derivatives based on benzothiazole were synthesized using a simple and green method. The synthesized compounds showed promising anti-inflammatory and inhibition activities. ADMET analysis revealed two molecules with potential for drug development.
Review
Chemistry, Multidisciplinary
Md. Azharul Arafath
Summary: Thiosemicarbazone Schiff base ligands have strong coordination and biological activity, and can form biologically active complexes with transition metals.
JOURNAL OF SULFUR CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Saeedeh Kamalinahad, Esmail Vessally
Summary: This study utilized DFT calculations to evaluate the interaction between the surface of a B-22 nanocluster decorated with Sc and Ti atoms and SO2 gas as a chemical sensor. The results showed that the decorated M/B-22 structure exhibited promising sensing properties for the detection of SO2 gas.
JOURNAL OF SULFUR CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Athandwe M. Paca, Saheed O. Benson, Amos A. Fatokun, Peter A. Ajibade
Summary: Four organoruthenium(II) arene dithiocarbamate complexes were synthesized and characterized. The complexes showed promising cytotoxic effects against human cervical cancer and human lung fibroblast cell lines. Two compounds, C1 and C3, exhibited potent cytotoxicity and demonstrated potential as anticancer agents.
JOURNAL OF SULFUR CHEMISTRY
(2024)
Article
Chemistry, Multidisciplinary
Emine Ozturk, Elif Subasi, Ece Su Cakmakci, Asli Sahiner, Betuel Sen Yuksel
Summary: A series of thiosemicarbazones containing benzothiophen moiety were synthesized and characterized. These compounds exhibited higher efficacy against gram-positive bacteria and lower antifungal activity against C. albicans.
JOURNAL OF SULFUR CHEMISTRY
(2024)
