Catalytic Addition of Simple Alkenes to Carbonyl Compounds by Use of Group 10 Metals
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Lewis Acid Mediated Reactions of Olefins with Carbonyls
Lewis Acid Mediated Reactions of Olefins with Carbonyls Submitted by Stephen Flower For the Degree of PhD Of the University of Bath 2002 COPYRIGHT Attention is drawn to the fact that copyright of this thesis rests with its author. This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with its author and that no quotation from the thesis and no information derived from it may be published without the prior written consent of the author. This thesis may be made available for consultation within the University Library and may be photocopied or lent to other libraries for the purposes of consultation. …………………………..(signed) …………………………..(date) Abstract This thesis is divided into 5 chapters. The first chapter reviews the literature of Carbonyl-ene and Prins reactions. Recent advances in these areas and their application to natural product synthesis and other targeted syntheses are discussed. The second chapter discusses the concept of desymmetrisation using selected examples, including desymmetrising Carbonyl-ene reactions. Chapter Three introduces and discusses the work undertaken in studying the desymmetrising intramolecular carbonyl-ene of a meso-dialdehyde. Chapter Four details the concept of pyruvate-Prins cyclisation giving examples of its potential use. The chapter also gives examples of the use of rigid stereodefined scaffolds and their application. The chapter describes the reactivity of substituted pyruvate esters with cyclic enol ethers, and the elaboration of the cyclised products. The fifth chapter provides experimental details of the procedures reported. i Acknowledgements Many thanks to Dr Mike Willis for all his help and guidance and boundless enthusiasm over the years; and for a detailed investigation of the local pubs. -
BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics
W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2005 BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics Yajing Lian College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Inorganic Chemistry Commons Recommended Citation Lian, Yajing, "BI(III) Initiated Cyclization Reactions and Iodonium Fragmentation Kinetics" (2005). Dissertations, Theses, and Masters Projects. Paper 1539626842. https://dx.doi.org/doi:10.21220/s2-zj7g-fp23 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. BI(III) INITIATED CYCLIZATION REACTIONS AND IODONIUM FRAGMENTATION KINETICS A Thesis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Science by Yajing Lian 2005 APPROVAL SHEET This thesis is submitted in partial fulfillment of The requirements for the degree of Master of Science A Yajing Lian Approved by the Committee, December 20, 2005 Robert J. Hinkle, Chair Christopher Jl A] Robert D. Pike TABLE OF CONTENTS Page Acknowledgements VI List of Tables Vll List of Schemes V lll List of Figures IX Abstract XI Introduction Chapter I Secondary -
Accessing Light-Sensitive Polycyclic Aromatics Through an Alkynyl-Prins Cyclization
W&M ScholarWorks Undergraduate Honors Theses Theses, Dissertations, & Master Projects 4-2018 Accessing Light-Sensitive Polycyclic Aromatics through an Alkynyl-Prins Cyclization Daniel John Speer Follow this and additional works at: https://scholarworks.wm.edu/honorstheses Part of the Chemistry Commons Recommended Citation Speer, Daniel John, "Accessing Light-Sensitive Polycyclic Aromatics through an Alkynyl-Prins Cyclization" (2018). Undergraduate Honors Theses. Paper 1244. https://scholarworks.wm.edu/honorstheses/1244 This Honors Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Undergraduate Honors Theses by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. Accessing Light-Sensitive Polycyclic Aromatics through an Alkynyl-Prins Cyclization A thesis submitted in partial fulfillment of the requirement for the degree of Bachelor of Science with Honors in the Department of Chemistry from the College of William and Mary Accepted for Dr. Jonathan Scheerer Dr. Christopher Abelt Dr. Anne Rasmussen Directed by Dr. Robert J. Hinkle By Daniel John Speer April 26, 2018 Table of Contents Acknowledgements 3 Abstract 4 List of Figures 5 Introduction 6 Prins Chemistry and the alkynyl-Prins Cyclization 6 Photochromic Compounds 9 Cannabinoids 12 Results and Discussion 16 Development of Synthetic Procedure 16 Synthesis of Starting Material 17 Proposed Mechanism for the Cyclization 21 Synthesis and NMR Properties of Chromene Products 24 X-ray Crystallographic Analysis 27 UV/Visible Spectrophotometric Analysis 30 Conclusion 33 Experimental Methods 34 Materials and Methods 34 Synthetic Procedures 35 References 43 Supporting Information 46 Mass Spectrum of 11 46 X-ray Crystal Data and Structure Refinement for 11 47 2 Acknowledgements I would like to thank everyone involved in this process. -
Synthetic Strategies for the Lepadiformines and Cylindricine C Via Tandem Schmidt Reactions
Synthetic Strategies for the Lepadiformines and Cylindricine C via Tandem Schmidt Reactions By Angelica M. Meyer Submitted to the graduate degree program in the Medicinal Chemistry and the Graduate Faculty of The University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy. ________________________________ Chairperson: Jeffrey Aubé ________________________________ Dr. Thomas E. Prisinzano ________________________________ Dr. Ryan A. Altman ________________________________ Dean Kenneth L. Audus ________________________________ Dr. Paul R. Hanson Date Defended: December 5, 2011 The Dissertation Committee for Angelica M. Meyer certifies that this is the approved version of the following thesis: Synthetic Strategies for the Lepadiformines and Cylindricine C via Tandem Schmidt Reactions ________________________________ Chairperson Jeffrey Aubé Date approved: December 5, 2011 ii Abstract Marine flora and fauna have provided numerous alluring natural products, some of which contribute to treating diseases. The genus Clavelina is the source of a variety of tricyclic alkaloids, including the lepadiformine and cylindricine families. Novel approaches to synthesizing these molecules are sought after to increase their accessibility and for analogue development. In this dissertation, reaction sequences involving an intramolecular Schmidt transformation, which can quickly build up the molecular architecture associated with these targets is described. In one approach, the Lewis acid promoted intramolecular Schmidt reaction is combined in series with a Prins reaction to afford an interesting tricyclic lactam. This methodology culminates in a formal synthesis of lepadiformine A and a total synthesis of lepadiformine C. In another project, a tandem Diels–Alder/Schmidt reaction is utilized to prepare a similar tricyclic lactam. This process is applied toward an asymmetric total synthesis of (–)-cylindricine C. -
Intramolecular Ene Reactions of Functionalised Nitroso Compounds
INTRAMOLECULAR ENE REACTIONS OF FUNCTIONALISED NITROSO COMPOUNDS A Thesis Presented by Sandra Luengo Arratta In Partial Fulfilment of the Requirements for the Award of the Degree of DOCTOR OF PHILOSOPHY OF UNIVERSITY COLLEGE LONDON Christopher Ingold Laboratories Department of Chemistry University College London 20 Gordon Street London WC1H 0AJ July 2010 DECLARATION I Sandra Luengo Arratta, confirm that the work presented in this thesis is my own. Where work has been derived from other sources, I confirm that this has been indicated in the thesis. ABSTRACT This thesis concerns the generation of geminally functionalised nitroso compounds and their subsequent use in intramolecular ene reactions of types I and II, in order to generate hydroxylamine derivatives which can evolve to the corresponding nitrones. The product nitrones can then be trapped in the inter- or intramolecular mode by a variety of reactions, including 1,3-dipolar cycloadditions, thereby leading to diversity oriented synthesis. The first section comprises the chemistry of the nitroso group with a brief discussion of the current methods for their generation together with the scope and limitations of these methods for carrying out nitroso ene reactions, with different examples of its potential as a powerful synthetic method to generate target drugs. The second chapter describes the results of the research programme and opens with the development of methods for the generation of functionalised nitroso compounds from different precursors including oximes and nitro compounds, using a range of reactants and conditions. The application of these methods in intramolecular nitroso ene reactions is then discussed. Chapter three presents the conclusions which have been drawn from the work presented in chapter two, and provides suggestions for possible directions of this research in the future. -
Appendix I: Named Reactions Single-Bond Forming Reactions Co
Appendix I: Named Reactions 235 / 335 432 / 533 synthesis / / synthesis Covered in Covered Featured in problem set problem Single-bond forming reactions Grignard reaction various Radical couplings hirstutene Conjugate addition / Michael reaction strychnine Stork enamine additions Aldol-type reactions (incl. Mukaiyama aldol) various (aldol / Claisen / Knoevenagel / Mannich / Henry etc.) Asymmetric aldol reactions: Evans / Carreira etc. saframycin A Organocatalytic asymmetric aldol saframycin A Pseudoephedrine glycinamide alkylation saframycin A Prins reaction Prins-pinacol reaction problem set # 2 Morita-Baylis-Hillman reaction McMurry condensation Gabriel synthesis problem set #3 Double-bond forming reactions Wittig reaction prostaglandin Horner-Wadsworth-Emmons reaction prostaglandin Still-Gennari olefination general discussion Julia olefination and heteroaryl variants within the Corey-Winter olefination prostaglandin Peterson olefination synthesis Barton extrusion reaction Tebbe olefination / other methylene-forming reactions tetrodotoxin hirstutene / Selenoxide elimination tetrodotoxin Burgess dehydration problem set # 3 Electrocyclic reactions and related transformations Diels-Alder reaction problem set # 1 Asymmetric Diels-Alder reaction prostaglandin Ene reaction problem set # 3 1,3-dipolar cycloadditions various [2,3] sigmatropic rearrangement various Cope rearrangement periplanone Claisen rearrangement hirstutene Oxidations – Also See Handout # 1 Swern-type oxidations (Swern / Moffatt / Parikh-Doering etc. N1999A2 Jones oxidation -
Steam Cracking: Chemical Engineering
Steam Cracking: Kinetics and Feed Characterisation João Pedro Vilhena de Freitas Moreira Thesis to obtain the Master of Science Degree in Chemical Engineering Supervisors: Professor Doctor Henrique Aníbal Santos de Matos Doctor Štepánˇ Špatenka Examination Committee Chairperson: Professor Doctor Carlos Manuel Faria de Barros Henriques Supervisor: Professor Doctor Henrique Aníbal Santos de Matos Member of the Committee: Specialist Engineer André Alexandre Bravo Ferreira Vilelas November 2015 ii The roots of education are bitter, but the fruit is sweet. – Aristotle All I am I owe to my mother. – George Washington iii iv Acknowledgments To begin with, my deepest thanks to Professor Carla Pinheiro, Professor Henrique Matos and Pro- fessor Costas Pantelides for allowing me to take this internship at Process Systems Enterprise Ltd., London, a seven-month truly worthy experience for both my professional and personal life which I will certainly never forget. I would also like to thank my PSE and IST supervisors, who help me to go through this final journey as a Chemical Engineering student. To Stˇ epˇ an´ and Sreekumar from PSE, thank you so much for your patience, for helping and encouraging me to always keep a positive attitude, even when harder problems arose. To Prof. Henrique who always showed availability to answer my questions and to meet in person whenever possible. Gostaria tambem´ de agradecer aos meus colegas de casa e de curso Andre,´ Frederico, Joana e Miguel, com quem partilhei casa. Foi uma experienciaˆ inesquec´ıvel que atravessamos´ juntos e cer- tamente que a vossa presenc¸a diaria´ apos´ cada dia de trabalho ajudou imenso a aliviar as saudades de casa. -
Hydrocarbons Thermal Cracking Selectivity Depending on Their Structure and Cracking Parameters
Master in Chemical Engineering Hydrocarbons Thermal Cracking Selectivity Depending on Their Structure and Cracking Parameters Thesis of the Master’s Degree Development Project in Foreign Environment Cláudia Sofia Martins Angeira Erasmus coordinator: Eng. Miguel Madeira Examiner in FEUP: Eng. Fernando Martins Supervisor in ICT: Doc. Ing Petr Zámostný July 2008 Acknowledgements I would like to thank Doc. Ing. Petr Zámostný for the opportunity to hold a master's thesis in this project, the orientation, the support given during the laboratory work and suggestions for improvement through the work. i Hydrocarbons Thermal Cracking Selectivity Depending on Their Structure and Cracking Parameters Abstract This research deals with the study of hydrocarbon thermal cracking with the aim of producing ethylene, one of the most important raw materials in Chemical Industry. The main objective was the study of cracking reactions of hydrocarbons by means of measuring the selectivity of hydrocarbons primary cracking and evaluating the relationship between the structure and the behavior. This project constitutes one part of a bigger project involving the study of more than 30 hydrocarbons with broad structure variability. The work made in this particular project was focused on the study of the double bond position effect in linear unsaturated hydrocarbons. Laboratory experiments were carried out in the Laboratory of Gas and Pyrolysis Chromatography at the Department of Organic Technology, Institute of Chemical Technology, Prague, using for all experiments the same apparatus, Pyrolysis Gas Chromatograph, to increase the reliability and feasibility of results obtained. Linear octenes with different double bond position in hydrocarbon chain were used as model compounds. In order to achieve these goals, the primary cracking reactions were studied by the method of primary selectivities. -
Metal Catalyzed Outer Sphere Alkylations of Unactivated Olefins and Alkynes
Metal Catalyzed Outer Sphere Alkylations of Unactivated Olefins and Alkynes Stephen Goble Organic Super-Group Meeting Literature Presentation October 6, 2004 1 Outline I. Background • Introduction to Carbometallation • “Inner Sphere” vs. “Outer Sphere” • Review of Seminal Work II. Catalytic Palladium Systems III. Catalytic Platinum Systems IV. Catalytic Gold Systems 2 I. Background: Carbometallation is the formal addition of a metal and a carbon atom across a double bond. • Cis addition would involve olefin insertion in to an σ-alkyl-metal species. This is an “Inner Coordination Sphere” process. cis addition [M] [M] R olefin insertion R • The alkyl-metal species could arise from: 1. Oxidative addition of the metal to an electrophile. 2. Transmetallation of a nucleophile to the metal. 3. Direct nucleophilic attack on the palladium. • Trans addition would involve an “Outer Coordination Sphere” nucleophilic attack on the metal-olefin coordination complex. trans addition [M] [M] R- R 3 First Example: Carbopalladation of an Olefin Tsuji, J. and Takahashi, H. J. Am. Chem. Soc. 1965. 87(14), 3275-3276. [Pd] O O RO2C CO R PdCl2 RO OR 2 Na2CO3 [Pd] Cl • Amino and Oxo-palladations (i.e. Wacker Process) were previously known and have since been much more widely studied. • No distinction between cis and trans nucleophilic addition made. 4 Carbopalladation on Styrene: Different Modes of Attack Proposed different modes of attack based on different observed products with MeLi vs. Na-Malonate: Murahashi, S. et. al. J. Org. Chem. 1977. 42 (17), 2870-2874. Nucleophilic Attack on Pd Olefin Insertion B-Hydride Elimination CH3Li [Pd] [Pd] CH3 PdX2 CH3 [Pd]-H Inner Sphere Mechanism Palladium Coordination Nucleophilic Attack B-hydride elimination CO R CO2R 2 NaCH(CO2R) CO R [Pd] CO2R 2 PdX2 [Pd] [Pd]-H • Outer Sphere attack usually occurs at the more substituted carbon - more stabilization of + + charge (In intermolecular processes). -
Cyclopentane Synthesis
Cyclopentane Synthesis Dan O’Malley Baran Group Meeting Cyclopentane Synthesis Group Meeting O'Malley 2/9/2005 This presentation is broken down into the following catagories. Some reactions either fit more than one Students of organic chemistry are taught a number of reactions for the synthesis of category or do not fit easily into any of them. Efforts have been made to place all such reactions in the cyclohexanes at a very early stage of their careers. Techniques for the creation of cyclopentanes, most appropriate category. however, are generally taught at a much later stage and are rarely given the same detailed treatment. This may be the result of the fact that there are no equivalents of reactions such as the Diels-Alder and I. General Information Robinson Annulation in terms of generality, extent of use, and historical importance. This may, in turn, II. Ionic Reactions be caused by the fact that the cyclopentane is an inherintly "umpoled" functionality, as illustrated below. III. Metal Mediated Reactions IV. Radical Reactions FG V. Pericyclic and Pseudo-pericyclic Reactions VI. Ring Expansion and Contraction Reactions I. General Information This situation is further exacerbated by the general lack of cheaply available cyclopentane compounds Baldwin's rules in the chiral pool; wheras a number of cyclohexane terpenes are readily available for elaboration, there Baldwin has divided ring closure reactions into those that are "favored" and those that are "disfavored". are no analogous cylcopentane natural products. Cyclopentanes are however, present in many Those that are disfavored are not always impossible, but are frequently much more difficult to effect. -
Named Organic Reactions
Named Organic Reactions Thomas Laue and Andreas Piagens Technical University, Braunschweig, Germany Translated into English by Dr. Claus Vogel Universität Magdeburg, Germany JOHN WILEY & SONS Chichester • New York • Weinheim • Brisbane • Singapore • Toronto Contents Introduction ix Acyloin Ester Condensation 1 Aldol Reaction 4 Alkene Metathesis 10 Arbuzov Reaction 12 Arndt-Eistert Synthesis 13 Baeyer-Villiger Oxidation 16 Bamford-Stevens Reaction 19 Beckmann Rearrangement 22 Benzidine Rearrangement 24 Benzilic Acid Rearrangement 26 Benzoin Condensation 27 Bergman Cyclization 29 Birch Reduction 33 Blanc Reaction 36 Bucherer Reaction 37 Cannizzaro Reaction 40 Chugaev Reaction 42 Claisen Ester Condensation 45 Claisen Rearrangement 48 Clemmensen Reduction 52 Cope Elimination Reaction 54 Cope Rearrangement 56 Corey-Winter Fragmentation 59 Curtius Reaction 61 1,3-Dipolar Cycloaddition 64 [2 + 2] Cycloaddition 67 Darzens Glycidic Ester Condensation 71 Delepine Reaction 73 Diazo Coupling 74 Diazotization 77 Diels-Alder Reaction 78 vi Contents Di-7r-Methane Rearrangement 86 Dötz Reaction 88 Elbs Reaction 92 Ene Reaction 93 Ester Pyrolysis 97 Favorskii Rearrangement 100 Finkelstein Reaction 102 Fischer Indole Synthesis 103 Friedel-Crafts Acylation 106 Friedel-Crafts Alkylation 110 Friedländer Quinoline Synthesis 114 Fries Rearrangement 116 Gabriel Synthesis 120 Gattermann Synthesis 123 Glaser Coupling Reaction 125 Glycol Cleavage 127 Gomberg-B achmann Reaction 129 Grignard Reaction 132 Haloform Reaction 139 Hantzsch Pyridine Synthesis 141 Heck Reaction -
C9sc03756j1.Pdf
Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2019 Electronic Supplementary Information for Orthogonal Functionalization of Alternating Polyesters: Selective Patterning of (AB)n Sequences Ni Yi,a† Thomas T. D. Chen,a† Junjuda Unruangsri,b Yunqing Zhu,b and Charlotte K. Williamsa* a Chemistry researCh laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK b Department of Chemistry, Imperial College London, London, SW7 2AZ, UK †Joint first authors [email protected] TaBle of Contents SeCtion, Scheme, Table or Figure Pages Experimental SeCtion 3-6 Figure S1. StruCtures of the alternating polyesters P1-P9, all featuring internal and 4 terminal alkene funCtionalities. TaBle S1. Composition and Properties of P1-P9. 5 Scheme S1. One-pot hydroboration-oxidation reaCtion to Convert the polyester 5 terminal alkenes to alternating hydroxyl groups. Scheme S2. Photo-initiated thiol-ene reaCtions to transform the hydroxyl- 6 funCtionalized alternating polyesters into orthogonally funCtionalized (AB)n Polyesters TaBle S2. Preparation Data for Polymers P1(B) - P1(f) and data to aCCompany in Table 6 1. Figure S2. NMR speCtra for P1. 7 Figure S3. 2D NMR speCtra for P1. 8 1 Figure S4. H NMR speCtrum of polymer P1 (CDCl3, 500.0 MHz, 298 K). 9 13 1 Figure S5. C{ H} NMR speCtrum of P1 (d6-DMSO, 500.0 MHz, 298 K). 9 Figure S6. MALDI-ToF speCtrum of P1 synthesized with CHD as the CTA, (Table S1, #1). 10 TaBle S3. SEC CharaCterization data (in THF and DMF) for P1, P2 and P3.