Article
Chemistry, Organic
Jie Wang, Hui Qian, Shengming Ma
Summary: In this contribution, a palladium-catalyzed cross-coupling reaction was developed for the synthesis of conjugated allenynes. The reaction showed excellent efficiency and selectivity, resulting in high yields of diversely substituted allenynes. The synthetic method demonstrated potential utility in gram-scale reactions and synthetic transformations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Sara Gomez-Gil, Ruben Rubio-Presa, Raquel Hernandez-Ruiz, Samuel Suarez-Pantiga, Maria R. Pedrosa, Roberto Sanz
Summary: A new two-step procedure for the synthesis of 1,4-dicarbonyls has been developed using an efficient and clean Mo-catalyzed oxidative cleavage of cyclobutane-1,2-diols with DMSO as solvent and oxidant. The required starting glycols were prepared by nucleophilic additions of organolithiums and Grignard reagents to easily available 2-hydroxycyclobutanones.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yuan-Yuan Cheng, Ji-Xin Yu, Tao Lei, Hong-Yu Hou, Bin Chen, Chen-Ho Tung, Li-Zhu Wu
Summary: This study presents the first example of 1,2-dicarbonylation of alkenes by photocatalysis, achieving unsymmetric 1,4-dicarbonylation by tuning the reductive and electrophilic ability of the acyl precursor. The metal-free, redox-neutral and regioselective reaction shows great potential in biomolecular and drug molecular derivatization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Lin Li, Xin-Lian Liu, Zhuang Qi, Ai-Hua Yang, Ai-Jun Ma, Jin-Bao Peng
Summary: A palladium-catalyzed carbonylative Sonogashira/annulation reaction has been developed for the synthesis of indolo[1,2-b]isoquinolines, which establishes three C-C bonds and a C-N bond in one step.
Article
Chemistry, Organic
Bo-Wei Huang, Jeng-Liang Han
Summary: A vinylogous addition reaction of allyl aryl ketones can be catalyzed by squaramide catalysts to give good yields and excellent regioselectivity. Chiral tertiary alcohols and bicyclic pyrrolidones can be synthesized in good to excellent yields, enantioselectivities, and diaseteroselectivities. Experimental and DFT calculations suggest that the reaction favors 1,2-addition at lower temperatures and 1,4-addition/cyclization at higher temperatures. Compound 4 may form through either the 1,4-addition/cyclization pathway or retro-aldol reaction of compound 3, followed by subsequent 1,4-addition/cyclization.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hassan Farhid, Mohammad Taghi Nazeri, Mohammad Mahdi Rostami, Ahmad Shaabani, Behrouz Notash
Summary: This study developed an efficient and convenient approach for the synthesis of naphtho[1,2-f][1,4]oxazepine structures through consecutive Betti/Bargellini multicomponent reactions, producing novel oxazepine-based scaffolds with potential pharmaceutical interest from cheap and readily available starting materials in moderate yields.
Article
Chemistry, Applied
Ze-Jian Xue, Meng-Yao Li, Bin-Bin Zhu, Zhi-Tao He, Chen-Guo Feng, Guo-Qiang Lin
Summary: The palladium-catalyzed cross-coupling of ortho-vinyl aromatic bromides and olefins using a controllable 1,4-palladium migration/Heck cascade protocol is a mild, efficient, and highly stereoselective method for the synthesis of trisubstituted 1,3-dienes, especially triaryl-substituted ones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Rafaela G. Cabral, Goncalo Viegas, Rita Pacheco, Ana Catarina Sousa, Maria Paula Robalo
Summary: This study describes the sustainable synthesis, characterization, and evaluation of the electrochemical and biological properties of different substituted derivatives of 1,4- and 1,2-naphthoquinones (NQ). The synthesis of the derivatives was optimized using a microwave-assisted protocol, providing a more sustainable approach. The compounds were found to have potential anti-cancer activity against HepG2 cell lines and inhibitory action against AChE enzymes. Docking studies showed different binding interactions for the derivatives.
Article
Chemistry, Physical
An T. Ho, Seth C. Ensign, Evan P. Vanable, David Portillo, Jenna N. Humke, Gregory D. Kortman, Kami L. Hull
Summary: The Ir-catalyzed regioselective hydroamination of allyl amines and the catalyst-controlled regiodivergent hydroamination of homoallylic amines with aniline nucleophiles have been reported. These reactions can selectively synthesize diamines at different positions, and exhibit good reaction yields.
Article
Chemistry, Inorganic & Nuclear
Lukas Schuh, Ana Torvisco, Michaela Flock, Christa Grogger, Harald Stueger
Summary: In this study, the synthesis and reactivity of acyl-substituted 1,4-disilacydohexa-2,5-dienes are reported. Photolysis of compounds 4 and 5 leads to 1,3-Si -> O migration reactions, generating 1,4-disilacyclohexadienes with exocyclic Si=C bonds. Surprisingly, the reaction of compound 4 with (KOBu)-Bu-t followed by the addition of PhMe2SiCl results in the formation of silylated 1,4-disilanorbornadiene cages. The mechanism for this reaction was elucidated through calculations and the isolation and characterization of intermediate products.
Article
Chemistry, Organic
Chuan Wu, Qing-Han Li
Summary: A highly efficient route for synthesizing 1,2-disubstituted acetylene derivatives has been developed through nickel-catalyzed cross-couplings of alkynyl halides with aryl titanium reagents under mild conditions, leading to good to excellent isolated yields of up to 92%. The process is simple, easily performed, and provides an efficient method for the synthesis of 1,2-disubstituted acetylene derivatives.
Article
Chemistry, Organic
Juan J. Rojas, Elena Torrisi, Maryne A. J. Dubois, Riashat Hossain, Andrew J. P. White, Giovanni Zappia, James J. Mousseau, Chulho Choi, James A. Bull
Summary: This paper reports a method for synthesizing 1,4-dioxanes and explores the catalytic mechanism of the reaction. The reaction exhibits high regio- and diastereoselectivity, and the resulting products serve as interesting motifs for drug discovery.
Article
Chemistry, Organic
Diksha Rajput, Dolma Tsering, Muthu Karuppasamy, Kamal K. Kapoor, Subbiah Nagarajan, C. Uma Maheswari, Nattamai Bhuvanesh, Vellaisamy Sridharan
Summary: An efficient synthetic method for oxazepino[5,4-b]quinazolin-9-ones, 6H-chromeno[4,3-b]quinolines, and dibenzo[b,h][1,6]naphthyridines was established using a substrate-based approach under microwave-assisted and conventional heating conditions, achieving high yields (up to 88%). The one-pot process involved CuBr2-catalyzed cascade annulation and delivered oxazepino[5,4-b]quinazolin-9-ones with two new heterocyclic rings and three new C-N bonds. Microwave assistance was found to be superior, providing clean and rapid reactions completed in 15 minutes, compared to longer reaction times and elevated temperatures required for conventional heating.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Simiao Zhang, Xiaoxue Wang, Li-Li Han, Jibin Li, Zheng Liang, Donghui Wei, Ding Du
Summary: Atropisomers bearing multiple stereogenic axes have become increasingly important in material science, pharmaceuticals, and catalysis. However, the construction of multi-axis atropisomers with high stereoselectivity remains rare and challenging. In this study, a new class of 1,2-diaxially chiral triaryl alpha-pyranones was successfully synthesized in a single-step reaction, demonstrating broad substrate scope and excellent stereo-control. The success of this reaction can be attributed to the rational design of structurally matched reaction partners and the careful selection of the asymmetric catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Patricia Kriegelsteinova, Barbora Lemrova, Veronika Rucilova, Miroslav Soural
Summary: This article reports the synthesis of triazolo[1,5-a][1,4]diazepin-6-ones on solid support. Amino acids immobilized on Wang resin were modified and cyclized to yield the target compound, which was obtained in high purities and yields. The method was further applied to the solid-phase synthesis of oligopeptides containing the triazolodiazepinone moiety.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Alexander Schmer, Antonio Garcia Alcaraz, Andreas Wolfgang Kyri, Gregor Schnakenburg, Arturo Espinosa Ferao, Rainer Streubel
Summary: In this study, a set of azadiphosphiridine complexes were synthesized using N-H and P-H deprotonation as key steps. The P atoms in the complexes underwent a P-to-P' haptotropic shift, and the factors influencing the ring nitrogen geometry were investigated.
DALTON TRANSACTIONS
(2022)
Article
Biochemistry & Molecular Biology
Kazuhira Miwa, Shinobu Aoyagi, Takahiro Sasamori, Shogo Morisako, Hiroshi Ueno, Yutaka Matsuo, Hideki Yorimitsu
Summary: The reduction of fullerene (C-60) with sodium dispersion in the presence of an excess amount of dipropyl sulfate yields highly propylated fullerene, C-60(nC(3)H(7))(n) (max. n = 24), with C-60(nC(3)H(7))(20) being predominantly generated as indicated by mass spectrometry.
Article
Chemistry, Multidisciplinary
Alicia Rey Planells, Arturo Espinosa Ferao
Summary: The full chemical space of CHNO isomers and their related deprotonated CNO- anions is described for the first time, including the minimum energy structures and interconversions among them. The electronic structure of all isomers is analyzed using bond-strength-related descriptors and natural bond orbital analysis.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Takuya Murai, Yongning Xing, Mayu Kurokawa, Toshifumi Kuribayashi, Masanori Nikaido, Elghareeb E. Elboray, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Takeo Kawabata, Takumi Furuta
Summary: A one-pot transformation method has been developed to convert biaryl dicarboxylic acids to (NH)-phenanthridinone derivatives using Curtius rearrangement and subsequent basic hydrolysis. This method is also applicable for preparing optically active amide-functionalized [7]helicene-like molecules. In addition, aza[5]helicene derivatives with a phosphate moiety were obtained as products of the Curtius rearrangement step when chalcogen atoms were present in the substrates. X-ray diffraction analysis revealed that chalcogen-bonding and pnictogen-bonding interactions may contribute to the stabilization of these compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Sudhir Lima, Atanu Banerjee, Gurunath Sahu, Sushree Aradhana Patra, Kausik Sahu, Takahiro Sasamori, Giuseppe Sciortino, Eugenio Garribba, Rupam Dinda
Summary: In this study, five new mononuclear mixed ligand oxidovanadium(IV) complexes were synthesized and characterized. These complexes contain tridentate O,N,O-donor aroylhydrazones as the main ligand and N,N-chelating 2,2'-bipyridine and 1,10-phenanthroline as the co-ligand. The interaction of these complexes with two proteins was studied, and their cytotoxicity against human cervical cancer and colon cancer cell lines was evaluated.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Sushree Aradhana Patra, Gurunath Sahu, Pratikshya Das Pattanayak, Takahiro Sasamori, Rupam Dinda
Summary: In this study, five fluorescent organotin(IV) complexes based on ONO donors were successfully synthesized and their photophysical properties were characterized. The results showed that these compounds were easily absorbed by cells and mainly internalized in mitochondria with negligible cytotoxicity at imaging concentration. Additionally, these complexes exhibited high photostability and could be used for long-term real-time tracking of cell organelles. Therefore, this low-toxic organotin-based fluorescent probe has potential applications in imaging mitochondria and tracking changes in their morphology within living cells.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yusuke Oyamada, Shintaro Yamasaki, Mika Tsuzuki, Takumi Kitagawa, Masaru Kondo, Takahiro Sasamori, Shuichi Nakamura
Summary: The catalytic enantioselective allenylation of ketimines derived from isatins is reported. High regio- and enantioselective products were obtained using a bis(imidazoline)-palladium catalyst. The obtained products were further converted into various chiral amines. The stereoselectivity origin was revealed by DFT calculations of the transition state.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jan Fassbender, Niklas Volk, Antonio Garcia Alcaraz, Selvakumar Balasubramaniam, Arturo Espinosa Ferao, Rainer Streubel
Summary: After more than 160 years of research, scientists have finally synthesized an oxaphosphirane, a phosphorus analogue derivative of oxirane. Reactions with various compounds have shown that increasing the coordination number at phosphorus causes destabilization, which supports previous findings. Theoretical studies have provided insights into ring strain energy, ring/ring interconversion, and oxidation pathways.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Narumi Itoh, Koh Sugamata, Shogo Morisako, Shinobu Aoyagi, Hideki Yorimitstu, Takahiro Sasamori
Summary: A stable dibenzo-1,6,2,5-dioxadisilocine was synthesized and used as a difunctional electrophile for double-silylation reactions. Its molecular structure was characterized by spectroscopic means and single-crystal X-ray diffraction analysis. Unexpected silylated polycyclic compound was obtained through reductive coupling of phenanthrene via formal [3+3] dimerization reaction.
Article
Chemistry, Applied
Miriam Mas-Montoya, Antonio Garcia Alcaraz, Arturo Espinosa Ferao, Delia Bautista, David Curiel
Summary: Two four-coordinate boron complexes, compounds 5 and 7, were synthesized using similar benzophenanthridine-based ligands but with different conformational constraints, and their optical properties were investigated. Ligand design considering expansion of pi-conjugation and structural desymmetrization was found to be effective in obtaining fluorophores with large Stokes shifts. The incorporation of a conformationally free substructure increased the geometry relaxation in the first excited state (S1) and the ground state (S0), resulting in enhanced Stokes shift. Solvatochromism showed divergent behavior in emission and absorption spectra, attributed to the different stabilization degrees of the S0 and S1 states compared to the Franck-Condon states. Aggregation-induced emission (AIE) was observed in molecule 7, which was attributed to blocking the motion of peripheral rotor based on solid state packing determined by X-ray diffraction.
Article
Chemistry, Multidisciplinary
Arturo Espinosa Ferao, Alicia Rey Planells
Summary: Accurate ring strain energy (RSE) values were reported for sixty-six parent pnictogeniranes with two other identical p-block elements, El(2)Pn. A decrease in RSE was found to be correlated with an increase in the p character of the AO used in endocyclic bonds, particularly in groups 15 and 16. The higher -NICS(1) values also parallel the presence of atom-centred diatropic currents, mostly arising from the lone pairs. Only in the case of pnictogenaditrieliranes Tr(2)Pn (Tr=B, Al, Ga), the decrease of -NICS(1) is related to lower Huckel-type 2 pi-electron aromaticity in group 13.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Arturo Espinosa Ferao
Summary: This study explores the deoxygenation of parent and substituted oxiranes using lambda(3)sigma(3)-phosphorus reagents and reveals mechanistic aspects, as well as regio- and stereochemical consequences. It shows that attack to a ring C atom is usually preferred over direct P-to-O attack for one-step deoxygenation. The study also investigates the use of heavier derivatives AsMe3 and SbMe3 as oxirane deoxygenating reagents. The thermodynamic tendencies of lambda(3)sigma(3)-phosphorus reagents to act as oxygen or carbene acceptors are theoretically studied.
Article
Chemistry, Inorganic & Nuclear
Mridhul R. K. Ramachandran, Philipp C. Brehm, Gregor Schnakenburg, Takahiro Sasamori, Rene T. Boere, Rainer Streubel
Summary: Tricyclic 1,4-dihydro-1,4-phosphasilines 3a,b were synthesized from Si(NR2)(2)-bridged imidazole-2-thione compounds 2a,b. Based on the calculated Frontier Molecular Orbitals (FMOs) of 3b, a possible P-selective P-N bond cleavage reduction could be predicted, and a redox cycle was established using solutions of P-centred anionic derivative K[4b]. The cycle started with the oxidation of K[4b] to form the P-P coupled product 5b, which could be chemically reduced by KC8 to regenerate K[4b].
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Arif Ali Khan, Tim Kalisch, Arturo Espinosa Ferao, Rainer Streubel
Summary: The reaction of a transient terminal phosphinidene complex with triethylamine resulted in the formation of an sp(3) C-H insertion product, as confirmed by P-31 NMR spectroscopy. The product was isolated as a semi-solid compound. However, after 24 hours of reaction, a primary phosphane complex was obtained. The compounds were characterized using NMR spectroscopy and mass spectrometry. Formation of the final products is explained by a mechanistic proposal based on DFT calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Medicinal
Takuya Murai, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Takumi Furuta
Summary: The preparation, optical resolution, and structural investigations of a series of axially chiral biaryl dicarboxylic acids bearing oxygen, sulfur, and selenium atoms were conducted. The study revealed that the conformational control of these compounds can be achieved through chalcogen bonding interactions and tetrel bonding interactions. The physical and chiroptical properties of these biaryl dicarboxylic acids were also explored.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2022)
