Article
Chemistry, Multidisciplinary
Hayato Asanuma, Kazuya Kanemoto, Tokiharu Watanabe, Shin-ichi Fukuzawa
Summary: This study developed a new shelf-stable and easy-to-prepare bilateral disulfurating platform molecule, N-(morpholine-4-dithio)phthalimide, for the synthesis of unsymmetrical disulfides. The amino and imide leaving groups of this reagent can be orthogonally transformed. Under acidic conditions, the amino moiety can be displaced by various carbon nucleophiles, while the phthalimide moiety remains untouched. Meanwhile, the phthalimide leaving group undergoes substitution under basic or neutral conditions. The combination of these transformations allows for rapid access to diverse unsymmetrical disulfides through two C-S bond-forming reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Austin D. Marchese, Andrew G. Durant, Mark Lautens
Summary: A simple and modular approach using palladium catalysis to synthesize bis-heterocyclic spirocycles is reported. The method leverages a Mizoroki-Heck-type reaction to generate neopentylpalladium species, allowing for intramolecular C-H activation on a wide array of C-H bonds to produce a variety of spirocycles. The reaction is scalable, allowing for easy incorporation of biologically relevant heterocycles without the need for flash column chromatography.
Article
Chemistry, Inorganic & Nuclear
Michael S. M. Philipp, Rudiger Bertermann, Udo Radius
Summary: This study presents the Lewis acid/base adducts of N-heterocyclic carbenes (NHCs) with selected lead(ii) and lead(iv) compounds. The reaction products include various NHC-containing plumbylenes and plumbane adducts, as well as stable diaryl substituted plumbylenes which decompose in solution.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Grigory L. Kozhemyakin, Vladimir S. Tyurin, Alena O. Shkirdova, Evgeny S. Belyaev, Ekaterina S. Kirinova, Gelii Ponomarev, Alexey A. Chistov, Andrey Aralov, Victor A. Tafeenko, Ilya A. Zamilatskov
Summary: The study demonstrates carbene functionalization of porphyrinoids through metal-free thermal decomposition of their tosylhydrazones, resulting in the synthesis of tetrapyrrolyl carbenes and the formation of cyclopropane and cyclopentane derivatives. The stability and optical properties of the products were improved, and a new synthetic pathway for tailoring tetrapyrrolic macrocycles was established, allowing the obtainment of new tetrapyrrole derivatives.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Zahid Nawaz, Nevin Gurbuz, Muhammad Naveed Zafar, Muhammad Nawaz Tahir, Muhammad Ashfaq, Huseyin Karci, Ismail Ozdemir
Summary: The study successfully synthesized five new Pd PEPPSI-type complexes with NHC spectator ligands, which showed significant activity in direct arylation reactions. Structural details were further confirmed through single crystal X-ray diffraction study, showing good results with just 1 mol % catalyst loading in two hours.
Article
Chemistry, Multidisciplinary
Ying-Ai Wu, Rui-An Wang, Shu-Yun Jiang, Tai-Bai Jiang, Jun-Rong Song, Jun Shi, Wei Wu, Wei-Dong Pan, Hai Ren
Summary: In this study, a water-mediated electrochemical synthesis method was developed for the C3/C5-bromocyclization of tryptophol and tryptamine derivatives. By controlling the amount of water, the selective synthesis of 3a- or 5a-bromoindolines was achieved without the need for additional oxidants or additives.
Article
Chemistry, Multidisciplinary
Tuanli Yao, Rui Zhu, Tao Liu
Summary: In this study, a highly selective cyclocarboamination reaction was achieved using Zn(OTf)(2) as a catalyst, allowing for the synthesis of 3-aminoindenes with different substitution patterns. Furthermore, the complete reduction of iminoindenone intermediates led to the formation of cis-1-amino-2-arylindanes with excellent diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Yaru Jing, Jiahao Liu, Zongren Ye, Jiaqi Su, Yan Liu, Zhuofeng Ke
Summary: This study systematically investigates the unprecedented cooperation roles of NHC and CO ligands in N-heterocyclic carbene manganese complex promoted CO2 hydrogenation to formate. The results demonstrate the important cooperation role of the CO ligand in stabilizing the negatively charged hydride and assisting the reaction. The study provides important mechanistic insights into the rational design of bifunctional catalysts with conventional innocent ligands by uncovering the significant cooperation role of the often neglected CO ligand.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Bo Zhang, Yu'ai Duan, Xin Zhang, Shuai Guo
Summary: The study reveals a new type of NHC-to-azole rearrangement, in which both the carbene backbone and the substituent are non-innocent. This is the first example of NHC-to-azole rearrangements for aryl-substituted NHCs.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Samuel Nees, Henrik Beer, Philip Just, Leon M. Teichmeier, Leif E. Christoffer, Ailina Guljam, Kushik, Holger Braunschweig, Christian Hering-Junghans
Summary: We reported the synthesis of isolable and thermally stable phosphaalumenes (Ar)TerPAlCp* by combining a phosphinidene transfer agent (Ar)TerP(PMe3) with (Cp*Al)(4). Attempts to utilize Mes*P(PMe3) as a phosphinidene source with different Al(I) precursors did not yield phosphaalumenes, but the formation of the dimer [Cp*Al(mu-PMes*)](2) and C-H bond activation products indicated their intermediate formation.
Article
Chemistry, Organic
Zih-Siang Hong, Shih-Chieh Kao, Yu-Tsen Cheng, Chun-Jen Chen, Yen-Ku Wu
Summary: In this study, a photoflow method was developed for the radical-based coupling of unactivated arenes and aryl chlorides. The reaction proceeded smoothly at ambient temperature without the need for metal catalysts. Importantly, the reaction conditions were optimized for chloroarenes with different electronic properties. Despite the generally lower reactivity of aryl chlorides compared to their iodide and bromide counterparts, the developed protocol efficiently converted readily available and inexpensive chloroarenes into unsymmetrical biaryl products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Han Gao, Lingfei Hu, Yanlei Hu, Xiangying Lv, Yan-Bo Wu, Gang Lu
Summary: The origins of regioselectivity in Ni-catalyzed alkene hydrofunctionalizations were computationally investigated using energy decomposition analysis. The results indicate that the Markovnikov selectivity with aryl-substituted alkenes is favored due to the stabilizing charge transfer effect, while the anti-Markovnikov selectivity with alkyl-substituted alkenes is favored because of the destabilizing Pauli repulsion effect.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Tim P. P. Schlachta, Fritz E. E. Kuehn
Summary: Cyclic iron tetracarbenes are a class of macrocyclic iron N-heterocyclic carbene (NHC) complexes, inspired by heme analogs but with different electronic properties. The modification of their ligand framework allows control over the structural and electronic properties of the complexes. These iron tetracarbene complexes exhibit unique reactivity, involving the isolation of uncommon iron(iii) and iron(iv) species. They have been successfully applied in various catalytic reactions, such as C-H activation, CO2 reduction, aziridination, and epoxidation. This review provides insights for researchers to evaluate the properties of their complexes and optimize catalyst properties through ligand design.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
Xi-Chao Wang, Hao-Ran Wang, Xiufang Xu, Dongbing Zhao
Summary: The paper discusses the significance of investigating sila-8-membered ring fused biaryls for the discovery of new drug lead compounds. It presents a method for synthesizing these compounds through chemo- and regio-selective cross-dimerization of 5-membered palladacycles with silacyclobutanes under Pd-catalytic conditions. This method provides an efficient route for ring expansion to create the desired sila-8-membered ring fused biaryl skeletons.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Shang-You Sun, Selvam Raju, Guganchandar Vedarethinam, Pei-Lin Chen, Shih-Ching Chuang
Summary: The reaction of o-benzofulvene with TfOH leads to intramolecular cyclization through novel C-C and C-N bond formation, resulting in the formation of a new molecular framework with reasonable to excellent yields. The method tolerates various electron-withdrawing/donating substituents and exhibits high diastereoselectivity. Additionally, it is free of bases, oxidants, and metals, and proceeds under mild reaction conditions favorable for synthetic organic chemistry.
Review
Chemistry, Inorganic & Nuclear
Kritika Gour, Milan Kumar Bisai, Sakya S. Sen
Summary: Recent studies have utilized the sterically demanding hypersilyl group to stabilize unusual compounds with group 14 elements. These compounds are significant in terms of their structure and reactivity, and show potential for small molecule activation under ambient conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Moushakhi Ghosh, Nilanjana Sen, Shabana Khan
Summary: This review summarizes recent advances in heavier tetrylene-stabilized coinage metal complexes, primarily focusing on structure elucidation studies. These studies are expected to help design tetrylene ligand frameworks for future applications as photoemitters in organic light-emitting diode fabrication and efficient catalysts in homogeneous catalysis.
Article
Chemistry, Physical
Rohit Kumar, Vishal Sharma, Shailja Jain, Himanshu Sharma, Kumar Vanka, Sakya S. Sen
Summary: We report the synthesis of a calcium complex that acts as an efficient catalyst for the cyclotrimerization of various aromatic isocyanates under mild conditions. Single crystal X-ray studies on the complex revealed the presence of LiI, forming a four-membered ring with four different elements.
Article
Chemistry, Multidisciplinary
Rohit Kumar, Sayan Dutta, Vishal Sharma, Praval P. Singh, Rajesh G. Gonnade, Debasis Koley, Sakya S. Sen
Summary: In this study, two monomeric magnesium alkyl complexes were prepared using bis(phosphino)carbazole framework, and one of them (1) was utilized as a catalyst for the hydroboration of alkenes and alkynes with pinacolborane (HBpin). Various aromatic and aliphatic alkenes and alkynes were efficiently reduced. The study achieved anti-Markovnikov regioselective hydroboration and provided mechanistic insights through experimental investigations and DFT calculations. Additionally, the hydroboration protocol was successfully extended to terpenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Gargi Kundu, Kajal Balayan, Srinu Tothadi, Sakya S. Sen
Summary: This article presents a series of compounds obtained through chemical reactions, including experimental results with new structural features. These compounds are significant for understanding the properties of NHC cations and borinic acid cations.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ruksana Akhtar, Sandeep H. Kaulage, Mayur P. Sangole, Srinu Tothadi, Parameswaran Parvathy, Pattiyil Parameswaran, Kirandeep Singh, Shabana Khan
Summary: In this study, two new silylene-phosphine-based hybrid ligands were synthesized and used to prepare four-coordinate metal complexes. The redox and magnetic properties of these complexes were investigated using various experimental techniques and theoretical calculations. The results showed that the complexes exhibited paramagnetic behavior.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jabed Hossain, Nasrina Parvin, Brij Kumar Shah, Shabana Khan
Summary: In this study, bulky ligand supported chlorogermylene and chlorostannylene compounds were synthesized, and heavy ketones were obtained through reactions with elemental selenium and tellurium. The compounds were characterized using multinuclear NMR techniques and single-crystal X-ray diffraction studies.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Multidisciplinary
Milan Kumar Bisai, V. S. Ajithkumar, K. Vipin Raj, Kumar Vanka, Rajesh G. Gonnade, Sakya S. Sen
Summary: Compound 1 reacts with Me3SiCH(2)Cl to generate an unsymmetrical sp(2)-sp(3) disilene, 2, with the elimination of Me3SiCl. The reaction of compound 1 with PhC(NtBu)2SiCl undergoes oxidative addition of the C-Cl bond at the Si(II) atom, resulting in compound 3. Compound 2 reacts with sulfur and selenium to form compounds with Si=E (E=S (4) and Se (5)) double bonds. Tellurium reacts differently with compound 2 and forms a zwitterionic compound, 6.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Rohit Kumar, Vishal Sharma, Subhrashis Banerjee, Kumar Vanka, Sakya S. Sen
Summary: This study presents a transition metal-free method for the efficient and controlled reduction of isocyanates to formamide derivatives using pinacolborane as the hydrogenating agent and a magnesium methyl complex with a bis(phosphino)carbazole ligand as the catalyst. A wide range of substrates undergo selective hydroboration, yielding exclusively N-boryl formamides.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jabed Hossain, Jishnu Sai Gopinath, Srinu Tothadi, Pattiyil Parameswaran, Shabana Khan
Summary: In this study, the complexation reaction of silylene and germylene with copper(I) salts was demonstrated, and the resulting complexes were utilized as efficient catalysts in CuAAC reaction. The molecular structures of the copper complexes were determined through X-ray diffraction studies, and density functional theory studies revealed the catalytic mechanism.
Article
Chemistry, Inorganic & Nuclear
Sanjukta Pahar, Gargi Kundu, Christy P. George, Rajesh G. Gonnade, Sakya S. Sen
Summary: This article describes the coordination chemistry of the imidazolidin-2-imine ligand with aluminum. The reaction between the ligand and AlH3 yielded a dimeric aluminum dihydride. Substitution of hydride with various groups such as methyl, chloride, and bromide was achieved through different reactions. Additionally, reactions with different compounds led to the introduction of unusual functionalities onto alane.
Editorial Material
Chemistry, Physical
Moushakhi Ghosh, Shabana Khan
Article
Chemistry, Multidisciplinary
Rohit Kumar, Sanjukta Pahar, Joy Chatterjee, Soumya Ranjan Dash, Rajesh G. Gonnade, Kumar Vanka, Sakya S. Sen
Summary: In this study, two magnesium complexes supported by 2,2'-pyridylpyrrolide ligands (PyPyrH) were reported. These complexes exhibit bright luminescence with quantum yields of 22% and 14% in the solid state, respectively. Theoretical calculations indicate that their emissive properties originate from intra- and inter-ligand charge transfer.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Gargi Kundu, Ruchi Dixit, Srinu Tothadi, Kumar Vanka, Sakya S. Sen
Summary: The reaction of 6-SIDipp with different reagents has been studied, resulting in brominated products, adducts, and ring-expanded products.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Gargi Kundu, Srinu Tothadi, Sakya S. Sen
Summary: This paper describes the synthesis of SNHC-haloboranes adducts using a saturated five-membered N-Heterocyclic carbene, followed by nucleophilic substitutions to introduce unusual functional groups at the central boron atom. Different Lewis-base adducts were formed from the reaction with RBCl2, leading to the selective formation of NHC stabilized boric acid. Reactions with various reagents resulted in the formation of rare di-nitro substituted products and frustrated Lewis pair type small molecule activated products.
