Article
Chemistry, Organic
Muhua Wang, Linghua Zhang, Xi Chen, Xinying Zhang, Xuesen Fan
Summary: A novel synthesis of pyrazolidinone fused 1,3-benzooxazepine derivatives via a formal [4 + 3] annulation reaction of 1-phenylpyrazolidinones with diazonaphthalen-2(1H)-ones is presented. The mechanism involves an unprecedented reaction mode of 1-phenylpyrazolidinone, featuring cascade C-alkylation/C-annulation through C(sp(2))-H/C(sp(3))-H bond cleavage. Compared with literature methods, this protocol offers advantages such as easily accessible starting materials, structurally complex and biologically attractive products, a unique mechanistic pathway, and excellent chemo/regioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Run Li, Ye-Xing Hou, Ji-Hang Xu, Yang Gao, Xiao-Qiang Hu
Summary: A catalytic system-controlled divergent strategy has been developed for the precise synthesis of cinnolines and pyrazolo[1,2-a]cinnolines. This reaction exhibits remarkable features including simple operation, broad scope, and switchable fused N-heterocycle synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Jin Wang, Zhaoyang Li, Shengxin Bai, Qinghua Zhou, Tengteng Wu, Zhongyan Hu, Xianxiu Xu
Summary: This study presents an unprecedented [4 + 3] cycloaddition of furoketenimines with furocarbenoids for the efficient synthesis of cycloheptafuran and cycloheptapyrrole scaffolds. Zinc chloride acts as a promoter to form transient intermediates from isocyanides and ene-yne-ketones, and subsequently constructs a seven-membered ring. This three-component one-pot domino reaction sequentially constructs three rings and five bonds.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Wang Wang, M. Kevin Brown
Summary: In this study, we achieved the stereoselective construction of 3D bicyclic scaffolds and azetidine derivatives by modulating N-sulfonylimines, allowing for either [4+2]- or [2+2]-cycloaddition reactions. The utility of the method was demonstrated through further modulation of the resulting products. Mechanistic studies supported a reaction mechanism involving Dexter energy transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Mingying Wang, Yan Yuan, Caide Zhao, Shen Diao, Baorong Duan
Summary: A new curing system for high temperature vulcanized fluorosilicone rubber was studied using thermal cycloaddition reaction of trifluoroethylene aryl ether. The resulting Si-PFCB exhibits mechanical properties, thermal properties, and heat resistance comparable to ordinary high-temperature vulcanized silicone rubber, while the new curing system has the advantage of no vulcanizing agents and no by-products.
POLYMERS FOR ADVANCED TECHNOLOGIES
(2021)
Article
Chemistry, Organic
Daniel Schiavone, Diana M. Kapkayeva, Ryan P. Murelli
Summary: Oxidopyrylium [5 + 2] cycloaddition reactions are powerful strategies for constructing complex bicyclic architectures, but are often limited by competing dimerization processes. Recent studies have shown that oxidopyrylium dimers derived from 3-hydroxy-4-pyrones can revert back to ylides in situ, serving as clean ylide sources. The reaction between these dimers and stoichiometrically equivalent ratios of alkyne dipolarophiles under thermal conditions resulted in pure cycloadducts with specific alkynes, while less reactive alkynes led to lower yields due to dimer rearrangement and volatile alkynes produced competing ylide/alkyne cycloadducts with high regio- and stereoselectivities based on the source of the oxidopyrylium ylide.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Makoto Shimizu, Toshihiro Yamamoto, Hiroaki Shindo, Isao Mizota, Yusong Zhu
Summary: The compound 2,3-dimethoxy-2,3-dimethyl-1,4-dioxane serves as a stable precursor to functionalized cyclohexene derivatives through a [4+2] cycloaddition reaction, which can be transformed into potentially useful intermediates for biologically important materials.
Article
Chemistry, Organic
Fang Xie, Shijie Dong, Yajun Sun, Wenxing Liu, Xiaodan Liu, Lu Liu, Qin Zhao, Jiangli Wang
Summary: A CuH-catalyzed coupling reaction between aryl alkenes and 3-aryl-2H-azirines has been developed to synthesize optically active beta,beta-disubstituted ketones. The reaction proceeds via the regioselective attack of a chiral alkylcopper complex on the N-C2 bonds of azirines, generating chiral beta-aryl imines that can be further hydrolyzed to give ketones. This method provides a novel and efficient approach for the synthesis of chiral beta,beta-disubstituted ketones under mild conditions.
Article
Chemistry, Organic
Bipin Kumar Behera, Pallav Jyoti Arandhara, Bikoshita Porashar, Surjya Kumar Bora, Anil K. Saikia
Summary: A facile and efficient method for the synthesis of structurally diversified 2-pyridones using the [4 + 2] annulation of in situ generated azadienes from N-propargylamines and active methylene compounds is demonstrated. The reaction, promoted by an inorganic base, provides moderate to good yields. The developed methodology is applicable for the direct and formal synthesis of various bioactive molecules, with the synthetic utility further illustrated by late-stage functionalization of the products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Loic Groslambert, Andres Padilla-Hernandez, Robin Weiss, Patrick Pale, Victor Mamane
Summary: Tellurium species in the chalcogen series exhibit strong chalcogen bonding (ChB) interaction with electron-rich atoms, which has sparked renewed interest in tellurium-based derivatives for various applications. In this study, the catalytic activity of telluronium salts in the Povarov reaction is presented. Different dienophiles and imines efficiently react in the presence of diarylmethyltelluronium or triaryltelluronium salts as catalysts, and these catalysts can also perform the three-component Povarov reaction. The reactivity of telluroniums towards imines and aldehydes was confirmed through solid state and solution-state spectroscopy.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Xinyin Wu, Pan Gao, Feng Chen
Summary: The utilization of aryl radicals as open-shelled intermediates is important in synthetic chemistry, but current methods for generating aryl radicals are inefficient. Sulfonium salts have emerged as appealing sources for generating aryl radicals due to their unique structure and chemical tendencies. This review focuses on the mechanisms of cleaving C-S bonds in sulfonium salts to generate aryl radicals. The development of synthetic applications using aryl sulfonium salts as precursors is also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Gary C. George III, Kristin M. Hutchins
Summary: The crystal structure of a commercially available anthracene derivative, anthracene-9-thiocarboxamide, is reported for the first time. The compound undergoes a [4+4] cycloaddition in the solid state, which can be easily reversed using heat or mechanical force. The cycloadduct exhibits solvatomorphism and can self-assemble into different supramolecular structures. The compound can crystallize with various solvents and is capable of stabilizing vinyl-containing monomers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Seung Youn Hong, Alexander T. Radosevich
Summary: The study presents a catalytic approach to chemoselective primary amination of arylboronic acids, demonstrating an efficient synthesis strategy for versatile primary arylamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Hongliang Shi, Huachen Hou, Jinbo Duan, Jinwei Huang, Xiaoguang Duan, Xingang Xie, Huilin Li, Xuegong She
Summary: The total syntheses of Lycopodium alkaloids phleghenrines A and C have been achieved in 19 and 18 steps, respectively, using three (hetero)-Diels-Alder reactions and two ring-expansion reactions. A chiral precursor is prepared through an auxiliary controlled Diels-Alder reaction, enabling asymmetric synthesis. This strategy offers a general approach to synthesizing novel Lycopodium alkaloids.
Article
Chemistry, Multidisciplinary
Eric Bosch, Gregory M. Ferrence, Conrad J. Powell, Daniel K. Unruh, Herman R. Krueger, Ryan H. Groeneman
Summary: This study reports the formation of three co-crystals based on different halogen-bond donors and acceptors, where the different halogen bond formations between 1,4-diiodoperchlorobenzene and 1,4-diiodoperfluorobenzene lead to structural diversity in these co-crystals.
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, 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)
Article
Chemistry, Organic
Jesus de Maria Perez, Julio Puigcerver, Tainara Orlando, Aurelia Pastor, Marcos A. P. Martins, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: In this study, a series of succinamide-based hydrogen-bonded [2]rotaxanes with acyclic secondary amine as the catalytically active sites were synthesized and evaluated for their catalytic activity in an iminium-type process. The presence of an interlocked polyamide macrocycle notably increased the catalytic efficiency of the entwined organocatalysts by rapidly forming a reactive iminium intermediate with the aldehyde. The hydrogen-bonding interaction between the macrocycle and the electrophile plays a crucial role in the rapid formation and stabilization of the key intermediate.
ORGANIC CHEMISTRY FRONTIERS
(2021)
