DOCSLIB.ORG

Advanced Organic Synthesis

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

Advanced Organic Synthesis METHODS AND TECHNIQUES RICHARD S. MONSON DEPARTMENT OF CHEMISTRY CALIFORNIA STATE COLLEGE, HAYWARD HAYWARD, CALIFORNIA ACADEMIC PRESS New York and London COPYRIGHT © 1971, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORN BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY OTHER MEANS, WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS. ACADEMIC PRESS, INC. Ill Fifth Avenue, New York, New York 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. Berkeley Square House, London WlX 6BA LIBRARY OF CONGRESS CATALOG CARD NUMBER: 75-165531 PRINTED IN THE UNITED STATES OF AMERICA Contents Preface xi I. FUNCTIONAL GROUP MODIFICATIONS 1. Chemical Oxidations I. Chromium Trioxide Oxidation 3 II. Periodate-Permanganate Cleavage of Olefins 5 III. Free Radical Oxidation of an Allylic Position 7 IV. Epoxidation of Olefins 8 V. Baeyer-Villiger Oxidation of Ketones 9 VI. Lead Tetraacetate Oxidation of Cycloalkanols 11 VII. Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime 11 VIII. Oxidation of Ethers to Esters 12 IX. Partial Oxidation of an Aliphatic Side Chain 13 X. Bisdecarboxylation with Lead Tetraacetate 14 XI. Oxidation with Selenium Dioxide 15 References 16 2. Hydride and Related Reductions I. Reduction by Lithium Aluminum Hydride 18 II. Mixed Hydride Reduction 20 III. Reduction with Iridium-Containing Catalysts 22 IV. Reduction of Conjugated Alkenes with Chromium (H) Sulfate 23 References 24 3. Dissolving Metal Reductions I. Reduction by Lithium-Amine 25 II. Reduction by Lithium-Ethylenediamine 26 III. Reduction of a,/MJnsaturated Ketones by Lithium-Ammonia 27 IV. Reduction of a,/9-Unsaturated Ketones in Hexamethylphosphoric Triamide .... 28 V. Reduction of an a,/?-Unsaturated y-Diketone with Zinc 29 References 30 VI CONTENTS 4. Hydroboration I. Hydroboration of Olefins as a Route to Alcohols 32 II. Selective Hydroborations Using Bis(3-methyl-2-butyl)borane (BMB) 35 III. Purification of a Mixture of J9-10- and J1(9)-Octalins 37 References 38 5. Catalytic Hydrogenation I. Hydrogenation over Platinum Catalyst 39 II. Low-Pressure Hydrogenation of Phenols over Rhodium Catalysts 40 III. c/j-4-Hydroxycyclohexanecarboxylic Acid from /?-Hydroxybenzoic Acid 41 IV. 3-Isoquinuclidone from/7-Aminobenzoic Acid 42 V. Homogeneous Catalytic Hydrogenation 43 References 44 6. The Introduction of Halogen I. Halides from Alcohols by Triphenylphosphine—Carbon Tetrahalide 45 II. Halides from Alcohols and Phenols by Triphenylphosphine Dihalide 46 III. Allylic and Benzylic Bromination with W-Bromosuccinimide 48 IV. a-Bromination of Ketones and Dehydrobromination 49 V. Stereospecific Synthesis of /ra/w-4-Halocyclohexanols 51 References 52 7. Miscellaneous Elimination, Substitution, and Addition Reactions I. Methylenecyclohexane by Pyrolysis of an Amine Oxide 54 II. The Wolff-Kishner Reduction 55 III. Dehydration of 2-Decalol 56 IV. Boron Trifluoride Catalyzed Hydrolysis of Nitriles 56 V. Bridged Sulfides by Addition of Sulfur Dichloride to Dienes 57 VI. Methylation by Diazomethane 58 VII. Oxymercuration: A Convenient Route to Markovnikov Hydration of Olefins . ... 60 VIII. Esterification of Tertiary Alcohols 62 IX. Ketalization 63 X. Half-EsterificationofaDiol 64 XI. Substitution on Ferrocene 65 XII. Demethylation of Aryl Methyl Ethers by Boron Tribromide 66 References 67 CONTENTS VlI II. SKELETAL MODIFICATIONS 8. The Diels-Alder Reaction I. 3,6-Diphenyl-4,5-cyclohexenedicarboxylic Anhydride ........... 71 II. Reactions with Butadiene .................. 72 III. Catalysis by Aluminum Chloride ................ 74 IV. Generation of Dienes from Diones ................ 75 V. Reactions with Cyclopentadiene ................. 77 References ....................... 79 9. Enamines as Intermediates I. Preparation of the Morpholine Enamine of Cyclohexanone ......... 80 II. Acylation of Enamines ................... 81 III. Enamines as Michael Addition Reagents .............. 82 IV. Reactions of Enamines with j3-Propiolactone ............. 83 V. Reactions of Enamines with Acrolein ............... 84 References ....................... 86 10. Enolate Ions as Intermediates I. Ketones as Enolates: Car bethoxylation of Cyclic Ketones ......... 87 II. Esters as Enolates: 1,4-Cyclohexanedione and Meerwein's Ester ....... 90 III. Methylsulfinyl Carbanion as a Route to Methyl Ketones .......... 92 IV. Cyclization with Diethyl Malonate ................ 96 V. Carboxylations with Magnesium Methyl Carbonate (MMC) ......... 97 VI. Alkylation of j3-Ketoesters .................. 99 VII. The Robinson Annelation Reaction ................ 101 References ....................... 103 1 1 . The Wittig Reaction I. Benzyl-Containing Ylides .................. 104 II. Alkyl Ylides Requiring «-Butyl Lithium .............. 105 III. Methylsulfinyl Carbanion in the Generation of Ylides .......... 106 IV. The Wittig Reaction Catalyzed by Ethylene Oxide ........... 107 V. Cyclopropylidene Derivatives via the Wittig Reaction .......... 108 References ....................... 110 1 2 . Reactions of Trialkylbor anes I. Trialkylcarbinols from Trialkylboranes and Carbon Monoxide ........ Ill II. Dialkylketones from Trialkylboranes and Carbon Monoxide- Water ...... 112 III. The Reaction of Trialkylboranes with Methyl Vinyl Ketone and Acrolein ..... 114 IV. The Reaction of Trialkylboranes with Ethyl Bromoacetate ......... 115 References ....................... 115 Viil CONTENTS 13. Carbenes as Intermediates I. Carbene Addition by the Zinc-Copper Couple 116 II. Dibromocarbenes 117 III. Dihalocarbenes from Phenyl(trihalomethyl)mercury Compounds 119 References 120 14. Ethynylation I. Generation of Sodium Acetylide in Liquid Ammonia 121 II. The Generation of Sodium Acetylide in Tetrahydrofuran 123 III. The Generation of Sodium Acetylide via Dimsylsodium 124 References 125 15. Structural Isomerizations I. Acid Catalyzed Rearrangement of Saturated Hydrocarbons 126 II. Photolytic Ring Contraction 127 III. Isomerization of 1-Ethynylcylohexanol: Three Methods 129 IV. Photolytic Isomerization of 1,5-Cyclooctadiene 130 V. Oxidative Rearrangement of /3-Diketones 130 VI. Base Catalyzed Rearrangement of 4-Benzoyloxycyclohexanone 131 VII. Allenes from 1,1-Dihalocyclopropanes by Methyllithium 132 References 133 16. Elimination, Substitution, and Addition Reactions Resulting in Carbon-Carbon Bond Formation I. Carboxylation of Carbonium Ions 134 II. Paracyclophane via a 1,6-Hofmann Elimination 136 III. Diphenylcyclopropenone from Commercial Dibenzyl Ketone 137 IV. Phenylcyclopropane from Cinnamaldehyde 139 V. Conversion of Alkyl Chlorides to Nitriles in DMSO 140 VI. Photolytic Addition of Formamide to Olefins 141 VII. Intermolecular Dehydrohalogenation 142 VIII. Ring Enlargement with Diazomethane 143 IX. Conjugate Addition of Grignard Reagents 144 X. Dimethyloxosulfonium Methylide in Methylene Insertions 145 Xl. Acylation of a Cycloalkane: Remote Functionalization 147 XII. The Modified Hunsdiecker Reaction 149 References 150 CONTENTS IX 17. Miscellaneous Preparations I. Derivatives of Adamantane 151 II. Percarboxylic Acids 153 III. Diazomethane 155 IV. Trichloroisocyanuric Acid 156 References 157 Appendix 1. Examples of Multistep Syntheses 158 Appendix 2. Sources of Organic Reagents 161 Appendix 3. Introduction to the Techniques of Synthesis I. The Reaction 166 II. TheWorkup 175 III. Purification of the Product 178 References 188 Subject Index 189 Preface The developments in organic synthesis in recent years have been as dramatic as any that have occurred in laboratory sciences. One need only mention a few terms to under- stand that chemical systems that did not exist twenty years ago have become as much a part of the repertoire of the synthetic organic chemist as borosilicate glassware. The list of such terms would include the Wittig reaction, enamines, carbenes, hydride reductions, the Birch reduction, hydroboration, and so on. Surprisingly, an introduc- tion to the manipulations of these reaction techniques for the undergraduate or grad- uate student has failed to materialize, and it is often necessary for students interested in organic synthesis to approach modern synthetic reactions in a haphazard manner. The purpose of this text is to provide a survey, and systematic introduction to, the modern techniques of organic synthesis for the advanced undergraduate student or the beginning graduate student. An attempt has been made to acquaint the student with a variety of laboratory techniques as well as to introduce him to chemical reagents that require deftness and care in handling. Experiments have been drawn from the standard literature of organic synthesis including suitable modifications of several of the reliable and useful preparations that have appeared in "Organic Synthesis." Other examples have been drawn from the original literature. Where ever possible, the experiments have been adapted to the locker complement commonly found in the advanced synthesis course employing intermediate scale standard taper glassware. Special equipment for the performance of some of the syntheses would include low-pressure hydrogenation apparatus, ultraviolet lamps and reaction vessels, Dry Ice (cold finger) condensers, vacuum sublimation and distillation apparatus, and spectroscopic and chromato- graphic instruments. In general, an attempt has been made to employ as substrates materials that are available commercially at reasonable cost, although several of the experiments require precursor materials whose preparation is detailed in the text.
Recommended publications

  • The Degradation of Carboxylic Acid Salts by Means of Halogen the Hunsdieceerreaction Robert G

    THE DEGRADATION OF CARBOXYLIC ACID SALTS BY MEANS OF HALOGEN THE HUNSDIECEERREACTION ROBERT G. JOHNSON Department of Chemistry, Xavier University, Cincinnati 7, Ohio AND ROBERT K. INGHAM Department of Chemistry, Ohio University, Athens, Ohio Received November 17, 1966 CONTENTS I. Introduction.. ...... 11. Synthetic applicatio A. Aliphatic halides B. Alicyclic halides. C. Aromatic halides D. Heterocyclic hali 111. Materials and methods ....................................... 248 IV. Mechanisms., ...... V. Related reactions. ....... ......................................... 259 VI. Summary.. ......... VII. References.. ................................................................. 263 VIII. Addendum. ........................... .. 268 I. INTRODUCTION The degradation of a carboxylic acid salt in anhydrous medium by means of halogen to a halide of one less carbon atom than the original acid can be ex- pressed by the equation: RCOOM + Xz -+ RX + COz + MX Largely because of the extensive contributions of the Hunsdieckers (96, 97, 98, 99, 100, 101, 102) to our knowledge of this reaction, many chemists refer to the reaction under discussion as the “Hunsdiecker reaction.” Others designate the reaction by the names “silver salt reaction” or “silver salt-halogen reac- tion.” It has been proposed (95) that the name “Borodine reaction” be used, in recognition of the discovery of the reaction by Borodine (33). The authors of a recent book (179) incorrectly name this reaction M the Simonini reaction. The reviewers favor the use of “Hunsdiecker reaction,” if a name is to be given to this reaction, because of the many instances of the use of this termi- nology already in the literature and because of the large amount of developmental work carried out by the Hunsdieckers. The often-used descriptive names are contraindicated by the fact that the reaction is successful with salts other than silver salts, halogens other than bromine can be used, and the reaction of salts 219 220 ROBERT G.
  • 14.8 Organic Synthesis Using Alkynes

    14.8 Organic Synthesis Using Alkynes

    14_BRCLoudon_pgs4-2.qxd 11/26/08 9:04 AM Page 666 666 CHAPTER 14 • THE CHEMISTRY OF ALKYNES The reaction of acetylenic anions with alkyl halides or sulfonates is important because it is another method of carbon–carbon bond formation. Let’s review the methods covered so far: 1. cyclopropane formation by the addition of carbenes to alkenes (Sec. 9.8) 2. reaction of Grignard reagents with ethylene oxide and lithium organocuprate reagents with epoxides (Sec. 11.4C) 3. reaction of acetylenic anions with alkyl halides or sulfonates (this section) PROBLEMS 14.18 Give the structures of the products in each of the following reactions. (a) ' _ CH3CC Na| CH3CH2 I 3 + L (b) ' _ butyl tosylate Ph C C Na| + L 3 H3O| (c) CH3C' C MgBr ethylene oxide (d) L '+ Br(CH2)5Br HC C_ Na|(excess) + 3 14.19 Explain why graduate student Choke Fumely, in attempting to synthesize 4,4-dimethyl-2- pentyne using the reaction of H3C C'C_ Na| with tert-butyl bromide, obtained none of the desired product. L 3 14.20 Propose a synthesis of 4,4-dimethyl-2-pentyne (the compound in Problem 14.19) from an alkyl halide and an alkyne. 14.21 Outline two different preparations of 2-pentyne that involve an alkyne and an alkyl halide. 14.22 Propose another pair of reactants that could be used to prepare 2-heptyne (the product in Eq. 14.28). 14.8 ORGANIC SYNTHESIS USING ALKYNES Let’s tie together what we’ve learned about alkyne reactions and organic synthesis. The solu- tion to Study Problem 14.2 requires all of the fundamental operations of organic synthesis: the formation of carbon–carbon bonds, the transformation of functional groups, and the establish- ment of stereochemistry (Sec.
  • “Alkenyl Nonaflates from Carbonyl Compounds: New Synthesis, Elimination Reactions, and Systematic Study of Heck and Sonogashira Cross-Couplings”

    “Alkenyl Nonaflates from Carbonyl Compounds: New Synthesis, Elimination Reactions, and Systematic Study of Heck and Sonogashira Cross-Couplings”

    “Alkenyl nonaflates from carbonyl compounds: New synthesis, elimination reactions, and systematic study of Heck and Sonogashira cross-couplings” A thesis submitted to the Freie Universität Berlin for the degree of Dr. rer. nat. Faculty of Chemistry and Biochemistry 2009 Michael Alexander Kolja Vogel Department of Biology, Chemistry and Pharmacy FU Berlin 1. Gutachter: Prof. Dr. C. B. W. Stark 2. Gutachter: Prof. Dr. H.-U. Reißig Promotionsdatum: 19.06.2009 Contents Contents Contents 3 Abbreviations 7 Declaration and Copyright Statement 9 The Author 12 Acknowledgements 13 Abstract / Zusammenfassung 14 Introduction and Objective 16 Chapter 1 Alkenyl nonaflates from enolizable carbonyl precursors – 25 methodology, preparation, and elimination reactions 1.1. Purification of NfF and compatibility experiments with bases 26 1.2. Application of the internal quenching protocol for the 30 preparation of cyclic alkenyl nonaflates 1.3. Reactions of acyclic ketones with NfF and phosphazene bases 36 1.3.1 General remarks 36 1.3.2. Synthesis of alkynes: reactivity and selectivity 38 1.4. The formation of allenes 45 1.5. Conversion of aldehydes with NfF and phosphazene bases 50 1.5.1. Alkenyl nonaflate formation 50 1.5.2. Formation of terminal alkynes 52 1.6. Conclusions 54 Chapter 2 The alkenyl nonaflates in the Heck reaction – 56 methodology and reactivity 3 Contents 2.1. General remarks 57 2.2. Methodology and initial experiments 59 2.3. Systematic investigations 61 2.3.1. The solvent effect 61 2.3.2. The effect of different bases 65 2.3.3. The effect of additives 66 2.3.4. The effect of triphenylphosphine 71 2.3.5.
  • S1 Supporting Information Copper-Catalyzed

    S1 Supporting Information Copper-Catalyzed

    Supporting Information Copper-Catalyzed Semihydrogenation of Internal Alkynes with Molecular Hydrogen Takamichi Wakamatsu, Kazunori Nagao, Hirohisa Ohmiya*, and Masaya Sawamura* Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan Table of Contents Instrumentation and Chemicals S1 Characterization Data for Alkynes S1–S2 Procedure for the Copper-Catalyzed Semihydrogenation of Alkynes S2 Characterization Data for Alkenes S3–S5 References S5 NMR Spectra S6–S31 Instrumentation and Chemicals NMR spectra were recorded on a JEOL ECX-400, operating at 400 MHz for 1H NMR and 100.5 13 1 13 MHz for C NMR. Chemical shift values for H and C are referenced to Me4Si and the residual solvent resonances, respectively. Mass spectra were obtained with Thermo Fisher Scientific Exactive, JEOL JMS-T100LP or JEOL JMS-700TZ at the Instrumental Analysis Division, Equipment Management Center, Creative Research Institution, Hokkaido University. TLC analyses were performed on commercial glass plates bearing 0.25-mm layer of Merck Silica gel 60F254. Silica gel (Kanto Chemical Co., Silica gel 60 N, spherical, neutral) was used for column chromatography. Materials were obtained from commercial suppliers or prepared according to standard procedure unless otherwise noted. CuCl was purchased from Aldrich Chemical Co., stored under nitrogen, and used as it is. NatOBu, octane and 6-dodecyne 1a were purchased from TCI Chemical Co., stored under nitrogen, and used as it is. Diphenylacetylene 1j was purchased from Wako Chemical Co., stored under nitrogen, and used as it is. 1,4-Dioxane was purchased from Kanto Chemical Co., distilled from sodium/benzophenone and stored over 4Å molecular sieves under nitrogen.
  • Chapter 8 - Alkynes: an Introduction to Organic Synthesis

    Chapter 8 - Alkynes: an Introduction to Organic Synthesis

    Chapter 8 - Alkynes: An Introduction to Organic Synthesis Draw structures corresponding to each of the following names. 1. ethynylcyclopropane Answer: CCH 2. 3,10-dimethyl-6-sec-butylcyclodecyne Answer: 3. 4-bromo-3,3-dimethyl-1-hexen-5-yne CH3 Br Answer: H 2C CH C CH C C H CH3 4. acetylene Answer: H CCH Provide names for each compound below. CH3 5. CH3C CCHCH2CH2CH3 Answer: 4-methyl-2-heptyne CH 3 6. CCH Answer: 1-ethynyl-2-methylcyclopentane Test Items for McMurry’s Organic Chemistry, Seventh Edition 59 The compound below has been isolated from the safflower plant. Consider its structure to answer the following questions. H H CCCCCCCC H H3C C C C H H C H H 7. What is the molecular formula for this natural product? Answer: C13H10 8. What is the degree of unsaturation for this compound? Answer: We can arrive at the degree of unsaturation for a structure in two ways. Since we know that the degree of unsaturation is the number of rings and/or multiple bonds in a compound, we can simply count them. There are three double bonds (3 degrees) and three triple bonds (six degrees), so the degree of unsaturation is 9. We can verify this by using the molecular formula, C13H10, to calculate a degree of unsaturation. The saturated 13-carbon compound should have the base formula C13H28, so (28 - 10) ÷ 2 = 18 ÷ 2 = 9. 9. Assign E or Z configuration to each of the double bonds in the compound. Answer: H H E CCCCCCCCE H H3C C C C H H C H H 10.
  • The Chemistry of Alkynes

    The Chemistry of Alkynes

    14_BRCLoudon_pgs4-2.qxd 11/26/08 9:04 AM Page 644 14 14 The Chemistry of Alkynes An alkyne is a hydrocarbon containing a carbon–carbon triple bond; the simplest member of this family is acetylene, H C'C H. The chemistry of the carbon–carbon triple bond is similar in many respects toL that ofL the carbon–carbon double bond; indeed, alkynes and alkenes undergo many of the same addition reactions. Alkynes also have some unique chem- istry, most of it associated with the bond between hydrogen and the triply bonded carbon, the 'C H bond. L 14.1 NOMENCLATURE OF ALKYNES In common nomenclature, simple alkynes are named as derivatives of the parent compound acetylene: H3CCC' H L L methylacetylene H3CCC' CH3 dimethylacetyleneL L CH3CH2 CC' CH3 ethylmethylacetyleneL L Certain compounds are named as derivatives of the propargyl group, HC'C CH2 , in the common system. The propargyl group is the triple-bond analog of the allyl group.L L HC' C CH2 Cl H2CA CH CH2 Cl L L LL propargyl chloride allyl chloride 644 14_BRCLoudon_pgs4-2.qxd 11/26/08 9:04 AM Page 645 14.1 NOMENCLATURE OF ALKYNES 645 We might expect the substitutive nomenclature of alkynes to be much like that of alkenes, and it is. The suffix ane in the name of the corresponding alkane is replaced by the suffix yne, and the triple bond is given the lowest possible number. H3CCC' H CH3CH2CH2CH2 CC' CH3 H3C CH2 C ' CH L L L L L L L propyne 2-heptyne 1-butyne H3C CH C ' C CH3 HC' C CH2 CH2 C' C CH3 L L L L 1,5-heptadiyneLL L "CH3 4-methyl-2-pentyne Substituent groups that contain a triple bond (called alkynyl groups) are named by replac- ing the final e in the name of the corresponding alkyne with the suffix yl.
  • The Synthesis of a Polydiacetylene to Create a Novel Sensory Material

    The Synthesis of a Polydiacetylene to Create a Novel Sensory Material

    SELDE, KRISTEN A., M.S. The Synthesis of a Polydiacetylene to Create a Novel Sensory Material. (2007) Directed by Dr. Darrell Spells. 47pp. Sensory materials that respond to chemical and mechanical stimuli are under development in many laboratories. There are many significant uses of polydiacetylene compounds as sensory material. They have been applied to drug delivery, drug design, biomolecule development, cosmetics, and national security. In this study, experiments were carried out toward the development of a novel sensory material based on the established synthetic research on polydiacetylene compounds. Synthetic routes toward sensory materials with different head groups, different carbon chains lengths, and the incorporation of molecular imprints were explored. Diacetylene moieties, which can be used for polymer vesicle formation, were prepared by two main routes. In one route, 1-iodo-1-octyne and 1-iodo-1-dodecyne were prepared as starting materials for the synthesis of two diacetylene compounds (Diacetylene I and Diacetylene II). In the other route, a mesityl alkyne was used to prepare 5-iodo-1-pentyne, which was then used to prepare a triethylamino alkyne. This in turn was used to synthesize a diacetylene (Diacetylene III). Although each diacetylene product was formed, purification by column chromatography was found to be difficult. Experiments in vesicle formation, with and without molecular imprints, were also carried out using commercially available diacetylenes . THE SYNTHESIS OF A POLYDIACETYLENE TO CREATE A NOVEL SENSORY
  • The Molecular Level Modification of Surfaces: from Self-Assembled Monolayers to Complex Molecular Assemblies

    The Molecular Level Modification of Surfaces: from Self-Assembled Monolayers to Complex Molecular Assemblies

    University of Wollongong Research Online Australian Institute for Innovative Materials - Papers Australian Institute for Innovative Materials 1-1-2011 The molecular level modification of surfaces: From self-assembled monolayers to complex molecular assemblies J Justin Gooding University of New South Wales, [email protected] Simone Ciampi University of New South Wales, [email protected] Follow this and additional works at: https://ro.uow.edu.au/aiimpapers Part of the Engineering Commons, and the Physical Sciences and Mathematics Commons Recommended Citation Gooding, J Justin and Ciampi, Simone, "The molecular level modification of surfaces: From self- assembled monolayers to complex molecular assemblies" (2011). Australian Institute for Innovative Materials - Papers. 1853. https://ro.uow.edu.au/aiimpapers/1853 Research Online is the open access institutional repository for the University of Wollongong. For further information contact the UOW Library: [email protected] The molecular level modification of surfaces: From self-assembled monolayers to complex molecular assemblies Abstract The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers.
  • Hydrogenationn of 4-Octyne Catalyzedd by Pd[(M^W'- (CF3)2C6H3)) Bian](Ma) in THF

    Hydrogenationn of 4-Octyne Catalyzedd by Pd[(M^W'- (CF3)2C6H3)) Bian](Ma) in THF

    UvA-DARE (Digital Academic Repository) Palladium-catalyzed stereoselective hydrogenation of alkynes to (Z)-alkenes in common solvents and supercritical CO2 Kluwer, A.M. Publication date 2004 Link to publication Citation for published version (APA): Kluwer, A. M. (2004). Palladium-catalyzed stereoselective hydrogenation of alkynes to (Z)- alkenes in common solvents and supercritical CO2. General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl) Download date:04 Oct 2021 5 Kineti5 cc study and Spectroscopic Investigationn of the semi- hydrogenationn of 4-octyne catalyzedd by Pd[(m^w'- (CF3)2C6H3)) bian](ma) in THF 5.11 Introduction Homogeneouss hydrogenation by transition metal complexes has played a key role in the fundamental understandingg of catalytic reactions and has proven to be of great utility in practical applications.
  • Organic Seminar Abstracts

    Organic Seminar Abstracts

    L I B RA FLY OF THE U N IVERSITY OF 1LLI NOIS Q.54-1 Ii£s 1964/65 ,t.l P Return this book on or before the Latest Date stamped below. Theft, mutilation, and underlining of books are reasons for disciplinary action and may result in dismissal from the University. University of Illinois Library OCfcfcsrm L161— O-1096 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/organicsemi1964651univ s ORGANIC SEMINAR ABSTRACTS 196^-65 Semester I Department of Chemistry and Chemical Engineering University of Illinois ' / SEMINAR TOPICS I Semester I96U-I965 f"/ ( Orientation in Sodium and Potassium Metalations of Aromatic Compounds Earl G. Alley 1 Structure of Cyclopropane Virgil Weiss 9 Vinylidenes and Vinylidenecarbenes Joseph C. Catlin 17 Diazene Intermediates James A. Bonham 25 Perfluoroalkyl and Polyfluoroalkyl Carbanions J. David Angerer 3^ Free Radical Additions to Allenes Raymond Feldt 43 The Structure and Biosynthesis of Quassin Richard A. Larson 52 The Decomposition of Perester Compounds Thomas Sharpe 61 The Reaction of Di-t -Butyl Peroxide with Simple Alkyl, Benzyl and Cyclic Ethers R. L. Keener 70 Rearrangements and Solvolysis in Some Allylic Systems Jack Timberlake 79 Longifolene QQ Michael A. Lintner 00 Hydrogenation ! Homogeneous Catalytic Robert Y. Ning 9° c c Total Synthesis of ( -) -Emetime R. Lambert 1* Paracyclophanes Ping C. Huang 112 Mechanism of the Thermal Rearrangement of Cyclopropane George Su 121 Some Recent Studies of the Photochemistry of Cross -Conjugated Cyclohexadienones Elizabeth McLeister 130 The Hammett Acidity Function R. P. Quirk 139 Homoaromaticity Roger A.
  • Development of a Solid-Supported Glaser-Hay Reaction and Utilization in Conjunction with Unnatural Amino Acids

    Development of a Solid-Supported Glaser-Hay Reaction and Utilization in Conjunction with Unnatural Amino Acids

    W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2015 Development of a Solid-Supported Glaser-Hay Reaction and Utilization in Conjunction with Unnatural Amino Acids Jessica S. Lampkowski College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Organic Chemistry Commons Recommended Citation Lampkowski, Jessica S., "Development of a Solid-Supported Glaser-Hay Reaction and Utilization in Conjunction with Unnatural Amino Acids" (2015). Dissertations, Theses, and Masters Projects. Paper 1539626985. https://dx.doi.org/doi:10.21220/s2-r9jh-9635 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]. Development of a Solid-Supported Glaser-Hay Reaction and Utilization in Conjunction with Unnatural Amino Acids Jessica Susan Lampkowski Ida, Michigan B.S. Chemistry, Siena Heights University, 2013 A Thesis presented to the Graduate Faculty of the College of William and Mary in Candidacy for the Degree of Master of Science Chemistry Department The College of William and Mary May, 2015 COMPLIANCE PAGE Research approved by Institutional Biosafety Committee Protocol number: BC-2012-09-13-8113-dyoung01 Date(s) of approval: This protocol will expire on 2015-11-02 APPROVAL PAGE This
  • Supporting Information

    Supporting Information

    Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2014 Supplementary Material Nickel-Catalyzed Substitution Reactions of Propargyl Halides with Organotitanium Reagents Qing-Han Li,a,b,* Jung-Wei Liao,a Yi-Ling Huang,a Ruei-Tang Chianga and Han-Mou Gaua,* a Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan b College of Chemistry and Environmental Protection Engineering, Southwest University for Nationalities, Chengdu 610041, China e-mail: [email protected] - S1- Table of Contents I. 1H and 13C NMR Spectra of Aryltitanium Reagents S3 1. (2-MeOC6H4)Ti(O-i-Pr)3 (4e) S3 2. (2,6-Me2C6H3)Ti(O-i-Pr)3 (4j) S5 II. 1H and 13C NMR Spectra of Coupling Products S7 1. 1-Phenyl-1,2-propadiene (2aa) S7 2. 1-(4-Methylphenyl)-1,2-propadiene (2ab) S9 3. 1-(2-Methylphenyl)-1,2-propadiene (2ac) S11 4. 1-(4-Methoxyphenyl)-1,2-propadiene (2ad) S13 5. 1-(2-Methoxyphenyl)-1,2-propadiene (2ae) S15 6. 1-(3,5-Dimethylphenyl)-1,2-propadiene (2af) S17 7. 1-(2-Naphthyl)-1,2-propadiene (2ag) S19 8. 1-(4-Trifluoromethylphenyl)-1,2-propadiene (2ah) S21 9. 1-cyclohexyl-1,2-propadiene (2ai) S23 10. 1-(2,6-Dimethylphenyl)-1,2-propadiene (2aj) S25 11. 1-(2,6-Dimethylphenyl)-4-(bromomethyl)-1,2,4-pentatriene (2aj’) S27 12. 3-Phenyl-1,2-pentadiene (2ba) S29 13. 3-(2-Methylphenyl)-1,2-pentadiene (2bc) S31 14. 3-(3,5-Dimethylphenyl)-1,2-pentadiene (2bf) S33 15. 3-(2,6-Dimethylphenyl)-1,2-pentadiene (2bj) S35 16.