Article
Chemistry, Multidisciplinary
Peter Ribar, Leos Valenta, Tomas Solomek, Michal Juricek
Summary: The nucleophilic addition of carbon-centered nucleophiles to nanographene ketones is a valuable late-stage method for functionalizing zigzag nanographenes, with potential for synthesizing and exploring previously unknown functionalized nanographenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Ronghui Huang, Minyan Wang, Hong Deng, Jingkai Xu, Hong Yan, Yue Zhao, Zhuangzhi Shi
Summary: In this study, an effective method for the synthesis of phosphacycles through nickel-catalyzed heteroannulation of internal alkynes with aminophosphanes derived from o-haloanilines was reported. The method exhibits a broad scope and allows the preparation of 2-λ5-phosphaquinolines with different steric and electronic properties for fine-tuning photophysical properties. Mechanistic studies provide insights into the heteroannulation pathway and reasons for stereospecificity.
Article
Chemistry, Multidisciplinary
Guolin Wu, Yuan Yao, Gen Li, Xue Zhang, Hui Qian, Shengming Ma
Summary: This study developed a catalytic recipe of copper halides to address the issues of side reactions and selectivity in the 1,5-H transfer of alka-1,4-diyn-3-yl amines, providing various allenynes with excellent enantioselectivities. The method was successfully applied to the first highly enantioselective total synthesis of the natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5-H transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yusuke Tomita, Naoto Haraguchi, Sayori Kiyota, Nobuyuki Komine, Masafumi Hirano
Summary: A traditional cobalt catalyst system has been found to exhibit previously undiscovered reactivity. Depending on the choice of tertiary phosphines and substrates, this catalytic system can catalyze diverse cycloadditions, yielding various cyclic compounds. The bite angles of the ligands used significantly contribute to the catalytic diversity.
Review
Chemistry, Applied
Supriya Rej, Amrita Das, Tarun K. Panda
Summary: The hydroboration of alkynes is a significant method for synthesizing important vinylborane compounds, with implications for regioselectivity and stereoselectivity. Extensive studies have been conducted on catalytic conditions and mechanistic studies to selectively obtain a single isomer, aiming to provide readers with accurate knowledge of available catalytic systems for this reaction. Researchers are encouraged to explore new catalytic systems to achieve the remarkable process of hydroboration of alkynes.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Saibal Singh, Graham E. Dobereiner
Summary: This study investigates the factors that control the selectivity of internal alkyne hydration using gold(I) catalysts and finds that the choice of solvent influences the selectivity. At ambient temperature, using [(IPr)Au(NCMe)][IMP-H] (C1) as a precatalyst is effective for the hydration of alkyl/alkyl and alkyl/aryl acetylenes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yuichi Kobayashi, Yuji Takashima, Yuuya Motoyama, Yukari Isogawa, Kyosuke Katagiri, Atsuki Tsuboi, Narihito Ogawa
Summary: This study investigated the regioselectivity and enantiospecificity of substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts. The results showed that under certain reaction conditions, highly selective products could be obtained.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Kjell Jorner, Tore Brinck, Per-Ola Norrby, David Buttar
Summary: The study introduces hybrid models combining traditional transition state modeling and machine learning to accurately predict reaction barriers, offering competitive accuracy in low-data scenarios.
Article
Chemistry, Applied
Shan-Shan Zhu, Heng Li, Rong Fu, Wen-Juan Hao, Shu-Liang Wang, Shu-Jiang Tu, Bo Jiang
Summary: The Lewis acid-catalyzed tricyclization method enables the efficient synthesis of rotationally hindered tribenzo[a,c,j]xanthenes, allowing scission/recombination of C-C triple bonds with good stereoselectivity and substituent compatibility.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Shubham Dutta, Akhila K. K. Sahoo
Summary: This paper describes a Pd-catalyzed three-component syn-1,2-arylmethylation method, which successfully synthesizes methyl-containing tetra-substituted olefins by using readily available and stable coupling partners iodo-arenes and methyl boronic acid. The reaction shows a broad scope with excellent functional-group tolerance and exhibits remarkable regio- and stereoselectivity. Biologically relevant motifs (BRM) bearing iodo-arenes and ynamides are also used for late-stage syn-1,2-arylmethylation of alkynes. Additionally, aryl-alkylation, aryl-trideuteriomethylation, alkynyl-methylation, and alkenyl-methylation of ynamides are presented, leading to the synthesis of synthetically important beta-amino-indenones and alpha-fluoro-alpha '-methyl ketones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Sagar Arepally, Ponnusamy Nandhakumar, Gisela A. Gonzalez-Montiel, Alina Dzhaparova, Gyeongho Kim, Ahyeon Ma, Ki Min Nam, Haesik Yang, Paul Ha-Yeon Cheong, Jin Kyoon Park
Summary: Electrochemical access to organometallic redox reagents allows for selective synthesis of various benzene derivatives with different regioisomers. A unified electrochemical strategy is presented for the selective cyclotrimerization of terminal alkynes to access both 1,3,5- and 1,2,4-regioisomeric trisubstituted benzene derivatives. The regiocontrol can be switched by the addition of a carboxylic acid.
Review
Chemistry, Applied
Krishna Biswas, Aniruddha Das, Venkataraman Ganesh
Summary: Organophosphorus catalysis has become a robust platform for introducing boron and silicon functionalities into organic substrates, providing efficient synthetic methodologies. Phosphorus compounds efficiently catalyze various reactions such as hydroboration and silylation in different organic substrates, with the classification of nucleophilic, electrophilic, and biphilic phosphorus catalysts.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Hepan Wang, Xiaoqiang Wu, Tao Xu
Summary: Transition-metal-catalyzed asymmetric carbon-carbon bond formation has been successful for the synthesis of phosphonates with an alpha-chiral carbon center through C(sp(3))-C(sp(3)) and C(sp(2))-C(sp(3)) couplings. However, the enantioselective C(sp)-C(sp(3)) coupling has not been reported. This study presents an unprecedented enantioconvergent cross-coupling of alkynyl bromides and alpha-bromo phosphonates to produce chiral alpha-alkynyl phosphonates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Cui-Cui Shan, Kai-Yang Dai, Meng Zhao, Yun-He Xu
Summary: A new protocol has been developed for the protoborylation and protosilylation of gem-difluoroallenes, allowing for the synthesis of a variety of organoboronates and silanes. This method is efficient and versatile, applicable to both mono- and disubstituted gem-difluoroallenes. The compounds obtained can be further converted into diverse organofluorine compounds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biodiversity Conservation
Yuan Sun, Cuiting Wang, Xinli Chen, Shirong Liu, Xingjie Lu, Han Y. H. Chen, Honghua Ruan
Summary: Phosphorus addition significantly decreases N:P and C:P ratios in plant, soil, and microbial biomass, but has negligible effects on C:N ratios. The effects of phosphorus addition become more evident with higher application rates and longer experimental duration, and do not vary with ecosystem types or climates. Changes in N:P and C:P ratios in soil and microbial biomass are associated with changes in soil pH and fungi:bacteria ratios.
GLOBAL CHANGE BIOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Ruben Zapata-Perez, Alessandra Tammaro, Bauke V. Schomakers, Angelique M. L. Scantlebery, Simone Denis, Hyung L. Elfrink, Judith Giroud-Gerbetant, Carles Canto, Carmen Lopez-Leonardo, Rebecca L. McIntyre, Michel van Weeghel, Alvaro Sanchez-Ferrer, Riekelt H. Houtkooper
Summary: NMNH, as a new NAD(+) precursor, significantly increases NAD(+) levels and reduces damage through a unique metabolic pathway. Administration of NMNH in mice leads to a rapid surge in NAD(+) levels, demonstrating its potential for treating acute kidney injury.
Article
Chemistry, Multidisciplinary
Carmen Lopez-Leonardo, Adrian Saura-Sanmartin, Marta Marin-Luna, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: This study describes the synthesis of chiral mechanically interlocked molecules and explores their applications in catalysis and sensing. The results demonstrate that enantioenriched value-added compounds can be obtained through base-promoted cyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Agriculture, Multidisciplinary
Carlos E. Iglesias-Aguirre, Fernando Vallejo, David Beltran, Elena Aguilar-Aguilar, Julio Puigcerver, Mateo Alajarin, Jose Berna, Maria Selma, Juan Carlos Espin
Summary: We report the discovery of two metabotypes associated with resveratrol metabolism by the human gut microbiota: LUNU (lunularin) producers and LUNU non-producers. The LUNU-producer metabotype can sequentially dehydroxylate resveratrol to yield LUNU and 4-hydroxydibenzyl, while the LUNU non-producer metabotype lacks this ability. These metabolites were detected in the urine and (or) feces of the majority of volunteers, but around 26% lacked the corresponding enzyme activity. Both metabotypes possess a 4-styrylphenol reductase that converts resveratrol to its corresponding dibenzyl.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Antonio Gonzalez-Sarrias, Juan Carlos Espin-Aguilar, Salvador Romero-Reyes, Julio Puigcerver, Mateo Alajarin, Jose Berna, Maria Victoria Selma, Juan Carlos Espin
Summary: This study investigated the antiproliferative activity of dietary resveratrol and its gut microbial metabolites in human colon cells. The results showed that microbial metabolism can affect the anti-cancer activity of resveratrol, and different molecular characteristics also have an impact on its activity.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Organic
Mateo Alajarin, Guillermo Cutillas-Font, Carmen Lopez-Leonardo, Raul-Angel Orenes, Marta Marin-Luna, Aurelia Pastor
Summary: This study presents the previously unknown intramolecular cyclization of a group of α-azido-ω-isocyanides in the presence of catalytic amounts of sodium azide. These compounds form tricyclic cyanamides [1,2,3]triazolo[1,5-a]quinoxaline-5(4H)-carbonitriles, while an excess of sodium azide leads to the formation of C-substituted tetrazoles through a [3 + 2] cycloaddition reaction. Experimental and computational methods were used to examine the formation of tricyclic cyanamides, revealing the presence of a long-lived N-cyanoamide anion that converts into the final cyanamide. The chemical behavior of these azido-isocyanides with an aryl-triazolyl linker was compared to that of a structurally identical azido-cyanide isomer. The synthetic procedures described in this work offer metal-free approaches to complex heterocyclic systems.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Jorge Lopez-Sanchez, Carmen Lopez-Leonardo, Aurelia Pastor, Jose Berna
Summary: This article describes an organic chemistry experiment in which a [2]rotaxane is synthesized through three- or five-component coupling reactions. The experiment aims to find the optimal reaction conditions for the synthesis and prove the interlocked nature of the rotaxane using NMR spectroscopy. The customizable nature of the experiment allows it to be adapted to a wide range of undergraduate course curricula.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Tomas Nicolas-Garcia, Aurelia Pastor, David Quinonero, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: This paper reports the synthesis of a ditopic interlocked building-block and its self-assembly into a cyclic dimer. NMR studies identified a cyclic hetero[4]pseudorotaxane as the main supramolecular structure in solution. Computational studies revealed that the assembly is the result of positive cooperativity in the hydrogen-bonding-driven assembly of this mechanically interlocked supramolecule. The disassembly of the cyclic dimer was achieved through a Diels-Alder reaction and competitive molecular recognition.
Article
Chemistry, Organic
Julio Puigcerver, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: In this study, the effect of gem-dimethyl substitution at the four benzylic carbons of the ring on the internal dynamics of two-station [2]rotaxanes is demonstrated. The structural modification of the polyamide macrocycles leads to a significant change in the internal dynamics, as revealed by variable-temperature H-1 NMR experiments. The shuttling rates of the octamethylated macrocycle along symmetrical threads were found to be much faster compared to the non-substituted ring, with the fumaramide-based system showing a rate 27 times faster than the model system.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
C. E. Iglesias-Aguirre, F. Vallejo, D. Beltran, J. Berna, J. Puigcerver, M. Alajarin, M. Selma, J. C. Espin
Summary: In this study, it was found for the first time that lunularin (LUNU) can be further dehydroxylated to yield 4-hydroxydibenzyl, a novel metabolite. However, (or) 3,4'-dihydroxy-trans-stilbene (DHST) was not further dehydroxylated.
Review
Chemistry, Multidisciplinary
Adrian Saura-Sanmartin, Aurelia Pastor, Alberto Martinez-Cuezva, Guillermo Cutillas-Font, Mateo Alajarin, Jose Berna
Summary: This review focuses on the chemistry of incorporating mechanical bonds into metal-organic frameworks (MOFs). The article first introduces the fundamental concepts of mechanically interlocked molecules (MIMs) and MOFs, then summarizes the advances in incorporating rotaxanes and catenanes into MOF matrices. The review concludes by discussing the dynamics of rotaxanes in MOFs and the operation of stimulus-responsive MIMs in MOFs, offering a critical opinion on the current state of the research field and suggesting key areas for future focus.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Jesus de Maria Perez, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: The catalytic activity of degenerate succinamide-based [2]rotaxanes can be modulated by changes at their macrocyclic component. The variation in catalytic efficiency is correlated with the electronics and dynamics of the entwined macrocycle.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Physical
Marta Castineira Reis, Mateo Alajarin, Marta Marin-Luna
Summary: This review summarizes theoretical and experimental studies on non-least-motion paths in chemical reactions, including dimerizations of carbenes and additional processes of reactive species like silylenes and carbynes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Marta Marin-Luna, Mateo Alajarin
Summary: Isocyanides are recognized as chameleonic compounds due to their versatile reactions with nucleophiles and electrophiles. When involved in homodimerization processes, some isocyanides exhibit superchameleonic behavior, with initially identical units taking on different roles along the reaction pathway. This study highlights the distinct differences between superchameleonic F-NC and standard Me-NC during their self-reaction, and suggests new examples of superchameleonic isocyanides.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
