HPB

Weaver G.W.

Chapter 4 4b Electrophilic Aromatic Substitution G. W. Weaver, G. W. Weaver Department of Chemistry, Loughborough University, Loughborough, Leicestershire, UKSearch for more papers by this author G. W. Weaver, G. W. Weaver Department of Chemistry, Loughborough University, Loughborough, Leicestershire, UKSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch4bBook Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary Functionalized arenes and heterocycles continue to serve as essential compounds in industry and academic research. Electrophilic aromatic substitution (EAS) remains one of the most important processes for introducing the diverse array of functionality required for new applications, and novel synthetic methods and investigations into the underlying mechanisms of EAS reactions continue to receive much attention. There is a growing use of artificial intelligence and machine learning to assist in identifying likely products of reactions or the best conditions to apply in synthesis. Improved methods for halogenation continue to be an important area of investigation in EAS. Studies on the mechanisms of new bromination methods continue to receive attention. Mechanisms for reactions to introduce sulfur-containing functionality have appeared. Metals are key to many electrophilic substitution processes as catalysts or stoichiometric reagents, and C–H insertion reactions feature prominently. References Makosza , M. , Chem. – Eur. 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Banerji K.K.

Coxon J.M.

Chapter 11 Molecular Rearrangements J. M. Coxon, J. M. Coxon Department of Chemistry and Physics, University of Canterbury, Christchurch, New ZealandSearch for more papers by this author J. M. Coxon, J. M. Coxon Department of Chemistry and Physics, University of Canterbury, Christchurch, New ZealandSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch11Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary A blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides has been reported from donor/acceptor diazoalkanes and propargyl sulfides to give functionalized allenes and is considered to occur via singlet carbene intermediates. A mechanism, named maleimide-assisted rearrangement and cycloaromatization, has been reported to trigger the reactivity of acyclic enediynes by a cascade 1,3-proton transfer processes to enable acyclic enediynes to undergo cycloaromatization. Computational studies have been reported to gain insights into the potential energy surfaces of competing Lewis-acid catalyzed carbonyl-ene, Prins, and carbonyl-olefin metathesis reactions. Computational studies on the origin of enantioselectivity in the semipinacol rearrangement of vinylogous alpha-ketol cocatalyzed by a cinchona-based primary amine and Bronsted acids indicate the reaction proceeds via complexation, nucleophilic addition, dehydration, carbon atom migration, enamine–imine tautomerization, imine hydrolysis, and Walden inversion. References Orlowska , K. , Rybicka-Jasinska , K. , Krajewski , P. , and Gryko , D. , Org. Lett. , 22 , 1018 ( 2020 ). 10.1021/acs.orglett.9b04560 CASPubMedWeb of Science®Google Scholar Yuan , H. 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J. , and Frongia , A. , Synthesis-Stuttgart , 53

Moloney M.G.

Parsons A.F., Parsons T.F.

Chapter 13 Radical Reactions A. F. Parsons, A. F. Parsons Department of Chemistry, University of York, Heslington, York, UKSearch for more papers by this authorT. F. Parsons, T. F. Parsons Wyke Sixth Form College, Hull, UKSearch for more papers by this author A. F. Parsons, A. F. Parsons Department of Chemistry, University of York, Heslington, York, UKSearch for more papers by this authorT. F. Parsons, T. F. Parsons Wyke Sixth Form College, Hull, UKSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch13Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary A review of photocatalytic strategies, involving radical intermediates of importance in organic synthesis, has appeared. The fact that photocatalytic cycles are composed of three steps, namely excitation, quenching, and finally restoration, is highlighted. The review has a particular emphasis on the restoration step, exploring how the deactivated form of the catalyst is converted back into the original state, which permits the cycle to start over again. It classifies photocatalytic processes according to what species is responsible for the restoration step, such as the substrate, an intermediate, or a sacrificial agent. The stereoselective bromoboration of acetylene with boron tribromide is investigated. The mechanism was studied by experiments and calculations, and besides the syn-addition mechanism (proceeding via a four-membered transition state) a radical and polar anti-addition mechanism was postulated. References Capaldo , L. , and Ravelli , D. , Eur. J. Org. Chem. , 2020 , 2783 (2020). 10.1002/ejoc.202000144 Google Scholar Lee , Y. and Kwon , M. S. , Eur. J. Org. Chem. , 2020 , 6028 (2020). 10.1002/ejoc.202000720 Google Scholar Yuan , Y. Q. , Majumder , S. , Yang , M. H. , and Guo , S. R. , Tetrahedron Lett. , 61 , 15106 ( 2020 ). Google Scholar Tang , H. T. , Jia , J. S. , and Pan , Y. M. , Org. Biomol. Chem. , 18 , 5315 ( 2020 ). 10.1039/D0OB01008A CASPubMedWeb of Science®Google Scholar Bartos , P. , Young , V. 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Dennis N.

Chapter 10 Addition Reactions: Cycloaddition N. Dennis, N. Dennis Stretton, Queensland, AustraliaSearch for more papers by this author N. Dennis, N. Dennis Stretton, Queensland, AustraliaSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch10Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary A review describing the synthesis of chiral spirooxindoles with quaternary stereogenic centers via 1,3-dipolar cycloaddition, Diels–Alder, and nucleophilic heterocyclic carbene reactions has been reported. A review of the synthesis of isoxazolines via iminoyl radical-initiated intramolecular cyclization, intermolecular radical addition-initiated cyclization, intramolecular nucleophilic cyclization, [3+2]-cycloaddition, and [2+2+1]-cycloaddition is presented. Molecular electron density theory (MEDT) investigations of the [3+2]-cycloaddition reactions of E-azomethine imines and 2-sulfolene show that the reaction follows a non-concerted two-stage one-step molecular mechanism. MEDT has been used to investigate the Grignard reagent-mediated [3+2]-cycloaddition reaction of phenyl azide with ethynylbenzene in the presence of ethyl magnesium bromide. References Ramirez , M. , Li , W. F. , Lam , Y. H. , Ghosez , L. , and Houk , K. N. , J. Org. Chem. , 85 , 2597 ( 2020 ). 10.1021/acs.joc.9b03340 CASPubMedWeb of Science®Google Scholar Shi , Y. J. , Liu , X. J. , Han , Y. , Yan , P. , Bie , F. S. , and Cao , H. , Tetrahedron Lett. , 61 , 151752 ( 2020 ). Google Scholar McVeigh , M. 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Bosque I., Gonzalez‐Gomez J.C.

Moreira V.M.

Chapter 5 Carbocations V. M. Moreira, V. M. Moreira Laboratory of Pharmaceutical Chemistry, Faculty of Pharmacy, University of Coimbra, Portugal Centre for Neuroscience and Cell Biology, University of Coimbra, Portugal Centre for Innovative Biomedicine and Biotechnology, University of Coimbra, PortugalSearch for more papers by this author V. M. Moreira, V. M. Moreira Laboratory of Pharmaceutical Chemistry, Faculty of Pharmacy, University of Coimbra, Portugal Centre for Neuroscience and Cell Biology, University of Coimbra, Portugal Centre for Innovative Biomedicine and Biotechnology, University of Coimbra, PortugalSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch5Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary A density-functional theory study of the reaction of butadiene with the allyl cation, in the gas phase and dimethyl sulfoxide, has brought to focus the fact that the widths of pathways to competing products in a reaction may be more relevant for determining the selectivity than barrier heights. The intermediacy of carbocations in studies including zeolites continued to be a topic of interest. The reactivity of the benzyl carbocation with benzene as a weak base was studied by quantitative infrared spectroscopy. The interconversion of cyclopropylcarbinyl and cyclobutyl cations is revisited using the concept of conformational landscape. The observation of the model hydrogen migration in carbocations using molecular dynamics calculations suggested that hydrogen migration velocity decreases with stronger electrostatic interactions between the hydrogen and neighbouring groups (drag concept) and that this property may be exploited for rationalizing previous experimental results and designing novel reactions. References Frontier , A. J. and Hernandez , J. J. , Acc. Chem. Res. , 53 , 1822 ( 2020 ). 10.1021/acs.accounts.0c00284 CASPubMedWeb of Science®Google Scholar Tsuji , H. and Kawatsura , M. , Asian J. Org. 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Kočovský P.

Moloney J.G., Moloney M.G.

Crampton M.R.

Bedford C.T.

Chapter 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives C. T. Bedford, C. T. Bedford Department of Chemistry, University College London, London, UKSearch for more papers by this author C. T. Bedford, C. T. Bedford Department of Chemistry, University College London, London, UKSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch2Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary Access to both stereoisomers of P-stereogenic phosphonothioates is provided by the chemoselective- and stereoselective alcoholysis of bi-2-naphthyl phosphonothioates. An internal nucleophilic catalyst-mediated cyclization for the synthesis of medium-sized lactones and lactams can be illustrated by the conversion in 90% yield of a bicyclic 9-hydroxyacid (30) into the 10-membered lactone (33) in CHCl3 at r.t. (Scheme 11). Activation of the carboxylic acid grouping of (30) by propanephosphonic acid anhydride (T3P) and diisopropylethylamine prompts the attack of it by the strategically located pyridine to form the N-acylium ion (31) which facilitates attack at C=O by the OH group to generate a TI (32), collapse of which forms the 10-membered lactone (33). References Allcock , H. R. and Walsh , E. J. , J. Am. Chem. Soc. , 94 , 4538 ( 1972 ). 10.1021/ja00768a021 CASWeb of Science®Google Scholar Movahed , F. S. , Sawant , D. N. , Bagal , D. 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L. , Wille , U. , and Hutton , C. A. , Chem. Eur. J. , 27 , 1620 ( 2020 ). 10.1002/chem.202005035 PubMedWeb of Science®Google Scholar Foden , C. S. , Islam , S. , Fernandez-Garcia , C. , Maugeri , L. , Sheppard , T. D. , and Powner , M. W. , Science , 370 , 865 ( 2020 ). 10.1126/science.abd5680 CASPubMedWeb of Science®Google Scholar Canavelli , P. , Islam , S. , and Powner , M. W. , Nature , 571 , 546 ( 2019 ). 10.1038/s41586-019-1371-4 CASPubMedWeb of Science®Google Scholar Organic Reaction Mechanisms 2020 ReferencesRelatedInformation

Birsa M.L.

Chapter 7 Carbanions and Electrophilic Aliphatic Substitution M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch7Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary Structure, reactivity, and synthetic applications of sodium diisopropylamide in enolization and orthometallation reactions are reviewed. The transfer of the electrophilic fragment from cumene hydroperoxide to the Zr(IV)-bound enolate has been accompanied by a heterolytic O—O bond cleavage. The formation of a hydrogen bond between the amine hydrogen atom(s) of the salen ligand and the hydroxy group of cumene hydroperoxide played a significant role in stabilizing the stereocontrolled transition state and improving the enantioselectivity. C-Alkylation of potassium enolates with styrenes (CAKES) is one of the highlighted reactions. Base-catalyzed amide CAKES have been studied using a synergistic approach of computation and experimental kinetic studies. The Schlenk equilibrium for thiophene Grignard reagents has been studied using quantum chemical reaction discovery tools. A detailed surface reaction mechanism of zinc-promoted silylation of phenylacetylene and chlorosilane has been reported based on combined experimental characterizations and periodic DFT calculations. References Woltornist , R. A. , Ma , Y. , Algera , R. 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A , 124 , 2029 ( 2020 ). 10.1021/acs.jpca.9b11991 CASPubMedGoogle Scholar Sun , Z. C. and Cundari , T. R. , Phys. Chem. Chem. Phys. , 22 , 24320 ( 2020 ). 10.1039/D0CP04080K CASPubMedWeb of Science®Google Scholar Khedkar , A. and Roemelt , M. , Phys. Chem. Chem. Phys. , 22 , 17677 ( 2020 ). 10.1039/D0CP02834G CASPubMedWeb of Science®Google Scholar Alburquerque , P. R. , Ramachandran , B. R. , Junk , T. , and Karsili , T. N. V. , J. Phys. Chem. A , 124 , 2530 ( 2020 ). 10.1021/acs.jpca.9b10892 CASPubMedWeb of Science®Google Scholar Voronin , V. V. , Ledovskaya , M. S. , Rodygin , K. S. , and Ananikov , V. P. , Org. Chem. Front. , 7 , 1334 ( 2020 ). 10.1039/D0QO00202J CASWeb of Science®Google Scholar Zhu , C. J. , Kuniyil , R. , Jei , B. B. , and Ackermann , L. , ACS Catal. , 10 , 4444 ( 2020 ). 10.1021/acscatal.9b05413 CASWeb of Science®Google Scholar Stockhammer , L. , Schorgenhumer , J. , Mairhofer , C. , and Waser , M. , Eur. J. Org. Chem. , 82 ( 2021 ). Google Scholar Chen , M. Y. , Pannecoucke , X. , Jubault , P. , and Besset , T. , Org. Lett. , 22 , 7556 ( 2020 ). 10.1021/acs.orglett.0c02750 CASPubMedWeb of Science®Google Scholar Organic Reaction Mechanisms 2020 ReferencesRelatedInformation

Birsa M.L.

Chapter 8 Elimination Reactions M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author M. L. Birsa, M. L. Birsa Faculty of Chemistry, "Al. I. Cuza" University of Iasi, Iasi, RomaniaSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch8Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary A unified framework for understanding nucleophilicity and protophilicity in the S N 2/E2 competition is described. The first palladium-N-heterocyclic carbene catalyzed Suzuki cross-coupling of aryl sulfoxides with phenylboronic acids is established. Density functional theory calculations have indicated that the reaction occurred through oxidative addition, transmetalation, and reductive elimination to provide the final coupling product. The synthesis of various functionalized alkynes from non-alkyne sources is overviewed in terms of its scope, limitations, and recent developments, especially elimination reactions. The mechanism of the photoreaction of azidomethyl methyl sulfide is investigated by a combined approach using low-temperature matrix isolation FTIR spectroscopy in conjunction with two theoretical methods. Lewis acid-assisted palladium-catalyzed dealkoxylation of N-alkoxyamides has been developed. The reaction proceeded with various N-alkoxyamides including a sulfonamide and a phosphoramide, in the absence of an external reductant. References Vermeeren , P. , Hansen , T. , Jansen , P. , Swart , M. , Hamlin , T. A. , and Bickelhaupt , F. M. , Chem. – Eur. 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