The Oxidation of Terminal Olefins to Methyl Ketones by Jones Reagent Is Catalyzed, by Mercury(Il)
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Wacker Oxidation ~Anti-Markovnikov~
Anti-Markovnikov Olefin Functionalization ~Prof. Robert H. Grubbs’ Work~ 4th Literature Seminar July 5, 2014 Soichi Ito (D1) Contents 1. Introduction • Flow of Prof. Grubbs’ Research • Markovnikov’s Rule • Wacker Oxidation 2. Grubbs’ Work • Substrate-Controlled Wacker Oxidation • Catalyst-Controlled Wacker-Type Oxidation 2 Introduction ~Flow of Research~ Olefin Metathesis Anti-Markovnikov Wacker Oxidation of Terminal Olefin Substrate-Controlled Wacker Oxidation of Internal Olefin Z-Selective Metathesis Hydration Ethenolysis + Reduction Hydroamination Z-Selective Ethenolysis Catalyst-Controlled Decarbonylative Dehydration Hydrophosphonation Production of Terminal Olefin Functionalization of Terminal Olefin 3 Introduction ~Markovnikov’s Rule~ Two-Step Two-Step (+1C) 4 Robert H. Grubbs et al. Science, 2011, 333, 1609. Anti-Markovnikov Hydration of Olefins • One-Step William C. Trogler et al. Science 1986, 233, 1069. This work was difficult to reproduce. Inorg. Chem. 1988, 27, 3151. • One-Step with Activated Olefins Robert G. Bergman and F. Dean Toste et al. J. Am. Chem. Soc. 2003, 125, 8696. Ben L. Feringa and Gerard Roelfes et al. Nat. Chem. 2010, 2, 991. • Three-Step 5 Shannon S. Stahl et al. J. Am. Chem. Soc. 2010, 132, 15116. Anti-Markovnikov Wacker Oxidation / Reduction Strategy Oxidation cycle must be compatible with the reduction cycle. aldehyde-selective Wacker Oxidation 6 Robert H. Grubbs et al. Science, 2011, 333, 1609. Introduction ~Wacker-Tsuji Oxidation~ • 1894 F. C. Phillips reported stoichiometric reaction. • 1959 J. Smidt et al. reported the Wacker process. (oxidation of ethylene to acetaldehyde) Investigations for convenient laboratory methods • 1976 J. Tsuji et al. reported PdCl2, CuCl / DMF, H2O method. “Terminal alkenes may be viewed as masked ketones.” 7 Jacques Muzart Tetrahedron 2007, 63, 7505. -
Alcohol Oxidation
Alcohol oxidation Alcohol oxidation is an important organic reaction. Primary alcohols (R-CH2-OH) can be oxidized either Mechanism of oxidation of primary alcohols to carboxylic acids via aldehydes and The indirect oxidation of aldehyde hydrates primary alcohols to carboxylic acids normally proceeds via the corresponding aldehyde, which is transformed via an aldehyde hydrate (R- CH(OH)2) by reaction with water. The oxidation of a primary alcohol at the aldehyde level is possible by performing the reaction in absence of water, so that no aldehyde hydrate can be formed. Contents Oxidation to aldehydes Oxidation to ketones Oxidation to carboxylic acids Diol oxidation References Oxidation to aldehydes Oxidation of alcohols to aldehydes is partial oxidation; aldehydes are further oxidized to carboxylic acids. Conditions required for making aldehydes are heat and distillation. In aldehyde formation, the temperature of the reaction should be kept above the boiling point of the aldehyde and below the boiling point of the alcohol. Reagents useful for the transformation of primary alcohols to aldehydes are normally also suitable for the oxidation of secondary alcohols to ketones. These include: Oxidation of alcohols to aldehydes and ketones Chromium-based reagents, such as Collins reagent (CrO3·Py2), PDC or PCC. Sulfonium species known as "activated DMSO" which can result from reaction of DMSO with electrophiles, such as oxalyl chloride (Swern oxidation), a carbodiimide (Pfitzner-Moffatt oxidation) or the complex SO3·Py (Parikh-Doering oxidation). Hypervalent iodine compounds, such as Dess-Martin periodinane or 2-Iodoxybenzoic acid. Catalytic TPAP in presence of excess of NMO (Ley oxidation). Catalytic TEMPO in presence of excess bleach (NaOCl) (Oxoammonium-catalyzed oxidation). -
New Reactions of Cyclic Oxygen, Nitrogen and Sulfur Acetal Derivatives
New Reactions of Cyclic Oxygen, Nitrogen and Sulfur Acetal Derivatives Samuel Edward Mann Supervisor Dr. Tom Sheppard A thesis submitted to University College London in partial fulfilment of the requirements for the degree of Doctor of Philosophy Declaration I, Samuel Edward Mann confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. ………………………… i Abstract Abstract This thesis describes the development of new reactions of cyclic oxygen, nitrogen and sulfur acetal derivatives and their applications in a diverse range of synthetic organic and organometallic chemistry. Detailed herein are advances in three main areas of acetal chemistry, namely: studies towards a new methodology for the synthesis of medium ring heterocycles; the use of thioacetals as directing groups for the palladium-mediated oxidation of olefins; and multi-component reactions for the synthesis of drug-like heterocyclic compounds. A brief overview of the chemistry of cyclic acetal derivatives is given in the first chapter, followed by a chapter on each of the three areas investigated. Relevant introductory literature is reviewed at the beginning of each chapter. Firstly, the ring expansion chemistry of unsaturated cyclic oxygen, nitrogen and sulfur acetal derivatives was explored for the development of a new methodology for the synthesis of medium ring heterocycles. This methodology has thus far proved unsuccessful in the synthesis of medium rings, although several interesting and unusual transformations were observed, such as the unexpected formation of an intriguing bicyclic enaminium salt. The use of thioacetals as directing groups for the palladium-mediated oxidation of terminal olefins was also explored, leading to the evolution of a new methodology for the catalytic, regioselective formation of either vinyl or allylic acetates. -
Organic Seminar Abstracts
Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/organicsemin1971752univ / a ORGANIC SEMINAR ABSTRACTS 1971-1972 Semester II School of Chemical Sciences Department of Chemistry- University of Illinois Urbana, Illinois 3 SEMINAR TOPICS II Semester 1971-72 Reactions of Alkyl Ethers Involving n- Complexes on a Reaction Pathway 125 Jerome T. Adams New Syntheses of Helicenes 127 Alan Morrice Recent Advances in Drug Detection and Analysis I36 Ronald J. Convers The Structure of Carbonium Ions with Multiple Neighboring Groups 138 William J. Work Recent Reactions of the DMSO-DCC Reagent ll+O James A. Franz Nucleophilic Acylation 1^2 Janet Ollinger The Chemistry of Camptothecin lU^ Dale Pigott Stereoselective Syntheses and Absolute Configuration of Cecropia Juvenile Horomone 1U6 John C. Greenfield Uleine and Related Aspidosperma Alkaloids 155 Glen Tolman Strategies in Oligonucleotide Synthesis 162 Graham Walker Stable Carbocations: C-13 Nuclear Magnetic Resonance Studies 16U Moses W. McMillan Organic Chlorosulfinates 166 Steven W. Moje Recent Advances in the Chemistry of Penicillins and Cephalosporins 168 Ronald Stroshane Cerium (iv) Oxidations 175 William C. Christopfel A New Total Synthesis of Vitamin D 18 William Graham Ketone Transpositions 190 Ann L. Crumrine - 125 - REACTIONS OF ALKYL ETHERS INVOLVING n-COMPLEXES ON A REACTION PATHWAY Reported by Jerome T. Adams February 2k 1972 The n-complex (l) has been described as an intermediate on the reaction pathway for electrophilic aromatic substitution and acid catalyzed rearrange- ment of alkyl aryl ethers along with sigma (2) and pi (3) type intermediates. 1 ' 2 +xR Physical evidence for the existence of n-complexes of alkyl aryl ethers was found in the observation of methyl phenyl ononium ions by nmr 3 and ir observation of n-complexes of anisole with phenol. -
Manipulating Selectivity and Reactivity in Palladium-Catalyzed Oxidation Reactions
Manipulating Selectivity and Reactivity in Palladium-Catalyzed Oxidation Reactions Thesis by Zachary Kimble Wickens In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2015 (Defended June 2nd, 2015) © 2015 Zachary Kimble Wickens All Rights Reserved 1 Dedicated to my parents for never pushing me to become a scientist 2 Acknowledgments The work I have the pleasure of sharing with you in this thesis would have been completely impossible without the help (both emotional and intellectual) of a tremendously large number of people. First, I want to thank my advisor, Bob Grubbs. I truly could not have asked for a more incredible thesis advisor. Since the beginning of my time at Caltech, you have subtly guided me towards the water but never forced me to drink. You have given me independence in choosing which projects to pursue and the directions these projects go, but always provided suggestions and hints along the way that have kept me on track. I know you will continue to provide great advice and strong support even long after I've left Caltech. Thanks for being my invisible safety net over the last five years. I would have never even considered pursuing a Ph.D in chemistry in the first place if it weren't for the fantastic chemistry faculty at Macalester College. Rebecca Hoye, Ronald Brisbois, Paul Fischer, Keith Kuwata, Thomas Varberg and Katherine Splan, you were all tremendously influential in my life. You taught me how to see the exciting puzzles that are scattered throughout the field of chemistry. -
Novel Co-Mo/MCM-41 Catalysts for Deep Hydrodesulfurization of Jet Fuel
Elucidating the mechanism of heterogeneous Wacker oxidation over response from Pd speciation (Figure 1) demonstrating for the first time that oxygen is activated Pd-Cu-exchanged zeolite Y via transient multi-edge XAS on copper in the heterogeneous system, which is similar to the homogeneous system. Increasing the O partial pressure led to a quick reoxidation of Cu(I) with a concomitant rapid 2 increase in CO formation while that of acetaldehyde proceeded more slowly. These results Jerick Imbao1,2, Jeroen van Bokhoven1,2*, Adam Clark1 and Maarten Nachtegaal1* 2 indicate that copper has more than one role as it does not only act as a co-catalyst for Pd(0) 1Paul Scherrer Institute, Villigen PSI (Switzerland) regeneration, but is also involved in the formation of CO byproduct. Without detecting the 2ETH Zurich, Zurich (Switzerland) 2 transient presence of Cu(0) and Pd(I), our results suggest that two one-electron transfers from *[email protected], [email protected] two Cu(II) ions to reoxidize Pd(0) to Pd(II) is at work in this heterogeneous Wacker catalyst. Introduction Low O (half order) High O (zero order) The homogeneous ethylene oxidation, called the Wacker process, is one of the most 1.00 2 1.00 2 efficient synthetic methods for manufacturing aldehydes. This process suffers from the difficulty in the separation of the products from the catalyst and from the high corrosivity and 0.75 0.75 formation of chlorinated byproducts associated with the excess use of HCl [1]. To overcome Cu(II) Cu(II) these problems many studies have been undertaken to design chloride-free heterogeneous 0.50 0.50 Cu(I) Cu(I) Wacker catalyst systems. -
Chromic Acid Oxidation of Hydrocarbons at The
CHROMIC ACID OXIDATION OF HYDROCARBONS AT THE BENZYLIC POSITION USING THE JONES REAGENT AND C-13 NMR STUDIES OF GEM-DIMETHYL INDANS AND -INDANONES By Radhika Rangarajan Ii Bachelor of Science Annamalai University Annamalai Nagar, India 1979 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY December, 1984 1hes\s )ti84 D ~ \°' U,£!- c.o p, ~ BENZYLIC POSITION USING THE JONES REAGENT AND C-13 NMR STUDY OF GEM-DIMTHYL INDANS AND -INDANONES Thesis Approved: (] . Dean of the Graduate College ii 1218538 •t ACKNOWLEDGMENTS I wish to begin with expressing my whole-hearted gratitude to Dr. E. J. Eisenbraun for his care and guidance during the course of this research. My committee members Dr. R. A. Bunce, Dr. E. M. Holt and Dr. E. C. Nelson have been very helpful in carefully evaluating this work. I appreciate all their help. I would like to thank Dr. T. Rangarajan, Dr. Pourahmady, Mr. Stan Sigle and Mr. Norm Perreira, who played an important role in this investigation. I acknowledge the financial support provided by the Oklahoma State University, Department of Chemistry, Department of Energy and Dow Chemical Company during my graduate tenure. I extend my deepest appreciation to my parents, Rangarajan and Shantha Rangarajan, without whose encouragement this study would not have been possible. A special thanks is due to Mrs. Lisa Thompson for typing my manuscript. iii TABLE OF CONTENTS Chapter Page I. INTRODUCTION AND HISTORICAL. 1 II. RESULTS AND DISCUSSION •• . 15 General •••••• . 15 Oxidation of Hydrocarbons •••••••• 19 Estimation of Solvent Consumption. -
Still More Carbonyl Chemistry
Lecture 17 Still More Carbonyl Chemistry March 26, 2019 Chemistry 328N Second Midterm Exam ⚫ When: Tomorrow, Wednesday, 3/27 ⚫ When: 7-9 PM (please do not be late) ⚫ Where: Painter 3.02!!! ⚫ What: Covers through last Thursday’s lecture ⚫ Remember: Homework problems!! ⚫ Please…bring pencils and an eraser no calculator and no phones …….Do a good job!!! Chemistry 328N Early Exam ⚫ Authorized students with exam conflict ⚫ When: 5-7 PM Tomorrow, 3/27 ⚫ Where: ETC 2.136 ⚫ Pencil and eraser no calculator and no phone ⚫ You must stay in the exam room until 7 PM Chemistry 328N Chromic Acid Oxidations Chemistry 328N Chemistry 328N Erin Brokovich ⚫ Hexavalent chromium compounds (including chromium trioxide, chromic acids, chromates, chlorochromates) are toxic and carcinogenic. Chemistry 328N Oxidation at Benzylic Positions O H H C OH H2SO4, K2CrO4 Heat KMnO4 in Base also works Chemistry 328N Selective Chromate Oxidations ⚫ Chromic acid and heat Oxidizes benzylic positions bearing at least one hydrogen to acids ⚫ Jones Reagent (H2CrO4 in acetone) takes primary alcohols to acids and secondary alcohols to ketones…The acetone keeps the reaction cool. Jones oxidation does not oxidize benzylic positions even with a hydrogen. ⚫ PCC (pyridinium chlorochromate) is weaker yet, it only oxidizes primary alcohols to aldehydes (!) and seconday alcohols to ketones. Chemistry 328N The Jones Oxidation Examples H2 SO4 H2 CrO4, Acetone OH OH O O O C C H2SO4 H OH H 2CrO4,Acetone H3C H3C OH O H2 CrO4, Acetone Chemistry 328N PCC Oxidations C5H5N + HCl + CrO3 → [C5H5NH][CrO3Cl] -
Improved Catalyst System for the Wacker Process
potential user’s site in container drums. The salts during the methanol drying technique, results from the trial, which should last for at then fast economic pay-back times can be anti- least 1000 hours of continuous operation, will cipated and a remarkably cheap hydrogen allow the viability of the process to be proven source deployed. J.E.P. at small cost, before a full size plant is commis- References sioned. I J. E. Philpott, Platinum Metals Rev., 1976, to, Where a trial is successful and when the (4), I 10; and references therein operating variables are established, including, 2 M. J. C(ole), Platinum Metals Rev., 1981,25, (I), I2 for example, the regularity of water rinsing 3 J. E. Philpott, Platinum Metals Rev., 1985, 29, necessary to prevent the build up of ammonium (I), 12; and references therein Improved Catalyst System for the Wacker Process The Wacker process for the palladium plete oxidation of ethylene to carbon dioxide catalysed conversion of ethylene to and water is avoided. acetaldehyde is one of the oldest industrial The authors have combined a number of con- homogeneous catalyst systems. The original cepts which have been available for some time, process was plagued by problems of corrosion and appear to have developed a system which within the reactor system, and has been replac- avoids most of the pitfalls associated with other ed by a heterogeneous catalyst system which catalyst systems for the Wacker process. If it suffers, however, from the problem of poor can be established that the catalyst maintains its catalyst utilisation. -
Alcohol Oxidations – Beyond Labz Virtual Chemlab Activity
Alcohol Oxidations – Beyond Labz Virtual ChemLab Activity Purpose: In this virtual experiment, you will be performing two oxidation reactions of benzyl alcohol, a primary alcohol. Primary alcohols can be oxidized to aldehydes or carboxylic acids, depending on the reagents used. You will be setting up oxidation reactions using chromic acid (H2CrO4) and pyridinium chlorochromate (PCC), and comparing the products of the two reactions. You will be monitoring the reactions using thin-layer chromatography (TLC) and analyzing IR and NMR spectra of the reactants and products. O further O OH oxidation oxidation H OH benzyl alcohol benzaldehyde benzoic acid Figure 1. Oxidation reactions of benzyl alcohol Introduction: Primary alcohols can be oxidized to aldehydes or carboxylic acids, depending on the reagents used. For many years, chromium reagents were commonly used for alcohol oxidations. Because of the toxicity of chromium-based reagents, many safer oxidizing agents have been developed and are more commonly used. As this lab is virtual, we can safely explore the reactivity trends for the older, chromium-based reagents. The two reaction conditions we will be exploring in this virtual experiment are: • Jones oxidation: This reaction uses chromic acid (H2CrO4) as the oxidizing agent. Chromic acid can be formed by dissolving sodium dichromate (Na2Cr2O7) or chromium trioxide (CrO3) in aqueous sulfuric acid (H2SO4). • PCC oxidation: This reaction uses pyridinium chlorochromate (PCC) in an anhydrous solvent, typically dichloromethane (CH2Cl2). The virtual lab does not give us CH2Cl2 as an option for a solvent, so we will substitute diethyl ether (CH3CH2OCH2CH3, or Et2O). Once your two virtual experiments are complete, you will decide which set of conditions oxidizes primary alcohols to aldehydes, and which oxidizes primary alcohols to carboxylic acids. -
17. Oxidation and Reduction Reactions 18
(11,12/94)(4,5/97)(02,3/07)(01/08) Neuman Chapter 17 Chapter 17 Oxidation and Reduction from Organic Chemistry by Robert C. Neuman, Jr. Professor of Chemistry, emeritus University of California, Riverside [email protected] <http://web.chem.ucsb.edu/~neuman/orgchembyneuman/> Chapter Outline of the Book ************************************************************************************** I. Foundations 1. Organic Molecules and Chemical Bonding 2. Alkanes and Cycloalkanes 3. Haloalkanes, Alcohols, Ethers, and Amines 4. Stereochemistry 5. Organic Spectrometry II. Reactions, Mechanisms, Multiple Bonds 6. Organic Reactions *(Not yet Posted) 7. Reactions of Haloalkanes, Alcohols, and Amines. Nucleophilic Substitution 8. Alkenes and Alkynes 9. Formation of Alkenes and Alkynes. Elimination Reactions 10. Alkenes and Alkynes. Addition Reactions 11. Free Radical Addition and Substitution Reactions III. Conjugation, Electronic Effects, Carbonyl Groups 12. Conjugated and Aromatic Molecules 13. Carbonyl Compounds. Ketones, Aldehydes, and Carboxylic Acids 14. Substituent Effects 15. Carbonyl Compounds. Esters, Amides, and Related Molecules IV. Carbonyl and Pericyclic Reactions and Mechanisms 16. Carbonyl Compounds. Addition and Substitution Reactions 17. Oxidation and Reduction Reactions 18. Reactions of Enolate Ions and Enols 19. Cyclization and Pericyclic Reactions *(Not yet Posted) V. Bioorganic Compounds 20. Carbohydrates 21. Lipids 22. Peptides, Proteins, and α−Amino Acids 23. Nucleic Acids ************************************************************************************** -
Transition Metal Catalysed Reactions for the Synthesis of Heteroaromatic Compounds
Transition Metal Catalysed Reactions for the Synthesis of Heteroaromatic Compounds Stephen Christopher Pelly A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg In fulfilment of the requirements for the Degree of Doctor of Philosophy January 2007 DECLARATION I declare that the work presented in this thesis was carried out exclusively by myself under the supervision of Professor C.B. de Koning. It is being submitted for the degree of Doctor of Philosophy in the University of the Witwatersrand, Johannesburg. It has not been submitted before for any degree or examination in any other University. _________________ 27th day of January, 2007 i ABSTRACT The carbazole and 2-isopropenyl-2,3-dihydrobenzofuran structures are widely found in many naturally occurring compounds. For example, the naturally occurring anti-cancer compound, rebeccamycin, contains an indolocarbazole core. Rotenone, which contains an (R)-2-isopropenyl-2,3-dihydrobenzofuran moiety, is widely used today as an effective naturally occurring pesticide. In the carbazole section of this thesis, the synthesis of the naturally occurring furanocarbazole, furostifoline is described. As key steps in this sequence, a Suzuki coupling reaction is utilised to couple appropriately functionalised indole and furan moieties. After further functional group transformations, a metathesis reaction is employed to construct the carbazole system, leading to furostifoline. The synthesis of the unnatural thio-analogue of furostifoline was similarly conducted and is described. Finally, in a somewhat different approach, the synthesis of the indolocarbazole core is described, utilising a Madelung approach initially to form the bis-indole system, 2,2’-biindolyl. After several functional group transformations, a metathesis reaction was once again successfully employed to form the carbazole system, thereby synthesising di(tert-butyl) indolo[2,3-a]carbazole-11,12-dicarboxylate.