Article
Chemistry, Multidisciplinary
Nicole Houszka, Hannes Mikula, Dennis Svatunek
Summary: 1,2,4,5-Tetrazines are widely used in bioorthogonal chemistry for their high reactivity in Diels-Alder reactions. The substituents in the 3- and 6-positions of the tetrazine scaffold significantly affect the rate of cycloadditions, but this is not explained by frontier molecular orbital interactions. Instead, the high reactivity of mono-substituted tetrazines is due to decreased Pauli repulsion, leading to a more asynchronous approach and reduced distortion energy. Additionally, ethylene is not a good model compound for other alkenes in Diels-Alder reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Casper Larsen Barlose, Jonas Faghtmann, Rene Slot Bitsch, Joseph Daniel Gbubele, Karl Anker Jorgensen
Summary: The combination of asymmetric organocatalysis with the (pseudo)-halogen effect allows for the efficient formation of chiral norcarane scaffolds. These scaffolds can easily undergo rearrangements or lactonization to form intricate chiral ring structures.
Article
Chemistry, Organic
Jian-Xiang Zhu, Fu Pi, Teng Sun, Wen-Yu Huang, Lu Gao, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: This article introduces a palladium-catalyzed tandem reaction that proceeds through sequential 2,4-dienylation/Michael addition/pi-sigma-pi isomerization/allylic alkylation. Using ortho-functionalized aryl enones and 2,4-dienyl carbonates as substrates, enantioenriched architectures with fused and spirocyclic frameworks are constructed in moderate to excellent yields and stereoselectivity. Importantly, the intrinsic intramolecular Diels-Alder reaction pattern of the dienylated intermediates is effectively reversed via Pd(0)-pi-Lewis base catalysis.
Article
Chemistry, Multidisciplinary
Jan Faehrmann, Gerhard Hilt
Summary: The study presents the acyl nitroso Diels-Alder reaction of 1,3-dienes with electrochemically oxidised hydroxamic acids. By utilizing alternating current electrolysis and optimizing the reaction conditions through Design of Experiments, high purity products were obtained with yields up to 96%, without the need for further purification.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhimei Mao, Aimin Huang, Lin Ma, Min Zhang
Summary: A facile visible light-promoted approach has been developed for the synthesis of anthracenone-furans from readily available 2,3-dibromonaphthoquinones and phenylbenzofurans via a formal Diels Alder reaction. This reaction involves wavelength-selective agitation of 4CzIPN, energy transfer to quinones, recombination of 1,6-biradicals, and elimination to give anthracenone-furans in good to excellent yields in one pot.
Article
Chemistry, Organic
Shuheng Xu, Linwei Zeng, Sunliang Cui
Summary: The Diels-Alder (DA) reaction and hetero-Diels-Alder (HDA) reaction are powerful methods for constructing carbocycles and heterocycles. This study presents an integrated building block that combines both DA and HDA reactions, utilizing triazenyl dienes to undergo the DA reaction and the newly released alkene moiety and triazene to engage in the HDA reaction.
Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Multidisciplinary
Khaled Youssef, Magali Allain, Thomas Cauchy, Frederic Gohier
Summary: 2-Bromo, 3-bromothiophene, 2,5-dibromothiophene, 3,4-dibromothiophene, and perbrominated thiophene were oxidized under different conditions to form thiophene S,S-dioxide. Depending on the substitution, sulfone was obtained when the hindered thiophene was used. However, monosubstituted thiophenes could not be transformed into sulfone due to the reactivity of the sulfoxide intermediate, which led to dimerization. The structures were confirmed through the obtaining of crystals. The oxidation of 3,4-dibromothiophene could either result in the formation of cycloadduct or the isolation of sulfone, which could further evolve into benzothiophene sulfone.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Guang-Chao Feng, Jun-Chi Li, Xiang Huang, Ji-Kai Liu, Bin Wu, Jin-Ming Yang
Summary: A novel cascade gold(I)-catalyzed hydroarylation of alkynylindoles and subsequent Diels-Alder cycloaddition with electron-deficient alkynes and alkenes is reported herein. The method features low catalyst loadings, high regioselectivity, broad functional group tolerances, access to important heterocycles, and 100% atom economy.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Hongling Wang, Qiangqiang Zhang, Shuai Xiao, Guanjie Wang, Xuan Huang, Xingkuan Chen, Junmin Zhang
Summary: We have developed a N-heterocyclic carbene (NHC) and base-mediated [3 + 3] annulation reaction for the synthesis of enantioselective dihydropyrano[3,2-b]indoles. Easily prepared sulfonium salts were used as precursors and reacted with unsaturated acyl azolium to achieve this transformation. The reaction conditions are mild and result in privileged indole-fused dihydropyranones with moderate to good yields and excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jonathan P. Knowles, Hannah G. Steeds, Maria Schwarz, Francesca Latter, Kevin Booker-Milburn
Summary: This method transforms simple starting materials into complex tetracyclic products with potential medicinal chemistry applications through a sophisticated chemical catalysis process.
Article
Chemistry, Multidisciplinary
Jesus Castro-Esteban, Florian Albrecht, Shadi Fatayer, Dolores Perez, Leo Gross, Diego Pena
Summary: The study successfully demonstrated an on-surface hexadehydro-Diels-Alder reaction at the single-molecule level using atomic force microscopy. This finding opens up new possibilities for introducing the concept of atom economy in the field of on-surface synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Huy Tran, Guillaume Revol, Alyson Poyser, Louis Barriault
Summary: In this study, a novel Lewis acid gold catalyst was used to generate synthetically challenging polycyclic scaffolds through a one-pot cascade sequence. By controlling the ligand and reaction conditions, both 6,6,5-tricyclic and 6,6,6,5-tetracyclic cores were selectively synthesized in one operation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Alemayehu Gashaw Woldegiorgis, Muhammad Suleman, Xufeng Lin
Summary: Asymmetric cycloaddition/annulation reactions have played a significant role in the synthesis of novel cyclic compounds for organic synthesis, natural product synthesis, material science, and chemical biology. Chiral phosphoric acid-catalyzed reactions have attracted attention in the synthetic community for the past two decades to develop new asymmetric reactions and synthesize complex molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Engineering, Environmental
Hao Li, Xin Xu, Xue Liu, Zhen Yao, Kun Cao
Summary: The research investigated the kinetics of 1,3-butadiene dimerization under high temperature and high pressure using a microchannel reactor. The study found that the dimerization reaction produced VCH and COD, with COD only forming under high temperature conditions. By fitting experimental data, apparent kinetic parameters for the dimerization under high pressure were obtained, showing that the reaction rate constants in the liquid phase were greater than in the gas phase.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Nicholas L. Magann, Mitchell T. Blyth, Michael S. Sherburn
Summary: The concise synthesis of alkaloid lythranidine utilizes the target's C-2 symmetry, adopting a two directional synthetic approach to efficiently access gram quantities of the natural product. The broad-spectrum nature of the synthesis is demonstrated through the preparation of three diastereomeric analogues of the natural product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Henning Hopf, Michael S. Sherburn
Summary: Allenes have traditionally played a minor role in Diels-Alder cycloadditions, but their importance has grown with their increased availability and unique stereochemical features. This review provides a comprehensive overview of allenes in Diels-Alder processes, covering their application in dienes, dienophiles, and cycloadducts, discussing both inter- and intramolecular cycloadditions, and describing the stereochemical aspects of the addition process. Emerging areas such as the use of allenic components in dehydro-Diels-Alder processes and dendralenic allenes for rapid generation of molecular complexity are also addressed, along with preparatively useful methods for allenic precursor synthesis.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Catherine A. McKenna, Maria Stiblarikova, Irene De Silvestro, Dominic J. Campopiano, Andrew L. Lawrence
Summary: The synthesis of chiral amines is a key reaction in chemical synthesis. Researchers are striving to develop more sustainable alternatives to metal-catalyzed methods currently used in various industries. By using N-phenylputrescine as an amine donor, a broad range of synthetically useful TA biocatalysts can be utilized under various reaction conditions, demonstrating its potential in practical applications like synthesizing pharmaceuticals such as sitagliptin.
Article
Chemistry, Multidisciplinary
Erin Westley, Madison J. Sowden, Nicholas L. Magann, Kelsey L. Horvath, Kieran P. E. Connor, Michael S. Sherburn
Summary: A general synthetic approach to molecular structures that are hybrids of tetraethynylethylene (TEE) and tetravinylethylene (TVE) is reported, with the potential for various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jiao Yu J. Wang, Mitchell T. Blyth, Michael S. Sherburn, Michelle L. Coote
Summary: This study conducted the first broad spectrum investigation into the photoenolization/Diels-Alder (PEDA) sequence, and found that substitution patterns have tolerance in the PEDA reaction, while thiocarbonyl derivatives react more slowly. The Diels-Alder reaction is predicted to have a broad scope, and CO undergoes a unique addition pathway.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Madeleine Stewart, Li-Juan Yu, Michael S. Sherburn, Michelle L. Coote
Summary: Benchmarked density functional theory is used to design and evaluate a series of novel atom transfer radical polymerization (ATRP) catalysts, among which the cage structure with 2-pyridyl arms performs the best. There are significant differences in catalytic performance among different stereoisomers, and the incorporation of electron donating groups improves ligand activity. Replacing 2-pyridyl arms with other neutral heterocycles does not offer much advantage, while ligands with negatively charged donor nitrogens can greatly enhance catalyst activity.
Article
Chemistry, Multidisciplinary
Robert C. Godfrey, Helen E. Jones, Nicholas J. Green, Andrew L. Lawrence
Summary: In this article, the research team discloses their detailed studies on the chemical feasibility of a proposed network of biosynthetic pathways towards the brevianamide family of bicyclo[2.2.2]diazaoctane alkaloids. Insights into issues of reactivity and selectivity in the biosynthesis of these structures have aided the development of a unified biomimetic synthetic strategy, resulting in the total synthesis of all known bicyclo[2.2.2]diazaoctane brevianamides and the anticipation of an as-yet-undiscovered congener.
Correction
Chemistry, Multidisciplinary
Belinda E. Hetzler, Dirk Trauner, Andrew L. Lawrence
NATURE REVIEWS CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Belinda E. Hetzler, Dirk Trauner, Andrew L. Lawrence
Summary: Natural product synthesis is one of the most vibrant and intellectually rewarding areas of chemistry. It serves as a platform for demonstrating elegant strategies, inventing new methods, and showcasing the effectiveness of established techniques. This review explores the fascinating aspect of natural product anticipation and investigates cases where laboratory synthesis precedes isolation from nature.
NATURE REVIEWS CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yi-Min Fan, Li-Juan Yu, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn
Summary: The diene-transmissive hetero-Diels-Alder sequences involving carbonyl dienophiles are reported for the first time. High enantioselectivities are achieved through the optimization of a Pd2+ catalyst system. The reaction generates fused polycyclic systems containing both heterocycles and carbocycles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jacob S. Bestwick, David J. Jones, Helen E. Jones, Panagiotis G. Kalomenopoulos, Rafal Szabla, Andrew L. Lawrence
Summary: A biomimetic synthetic strategy was used to synthesize (+/-)-ulodione A and predict two potential natural products. Computational investigations into biosynthetic selectivity guided the chemical synthesis. This work demonstrates the importance of biosynthetic considerations in guiding efficient synthetic strategies and anticipating new natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jessica E. Budwitz, Christopher G. Newton
Summary: pars-Quinones are widely used as targets and/or intermediates in various chemical and biological disciplines, highlighting the significance of efficient preparative methods. This Synpacts article provides an overview of ring forming approaches to para-hydroquinones and para-benzoquinones, concluding with our recent contribution on the development of 2,5-bis(tert-butyldimethylsilyloxy)furans as vicinal bisketene equivalents in the DieIs-Alder reaction.
Article
Chemistry, Multidisciplinary
Yi-Min Fan, Madison J. Sowden, Nicholas L. Magann, Erik J. Lindeboom, Michael G. Gardiner, Michael S. Sherburn
Summary: The first general synthesis of branched tetraenes ([4]dendralenes) and other related compounds has been achieved using a novel reaction method, with control over the stereoselectivity of the products. The broad applicability of this method opens up new opportunities for target-oriented synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tomas Vieira de Castro, David M. M. Huang, Christopher J. J. Sumby, Andrew L. L. Lawrence, Jonathan H. H. George
Summary: A concise method for the synthesis of a stereochemically complex compound, peshawaraquinone, from an achiral precursor, dehydro-alpha-lapachone, via unsymmetrical dimerization is reported. The formation of the compound involves reversible oxa-6 pi-electrocyclizations and base-catalyzed dimerization, resulting in the formation of six stereocenters through an intramolecular (3 + 2) cycloaddition. Combining the generation and in situ dimerization of dehydro-alpha-lapachone allows a one-step total synthesis of peshawaraquinone from lawsone and prenal.
Article
Chemistry, Organic
Jessica E. Budwitz, Christopher G. Newton
