DOCSLIB.ORG

Synthesis of Cyclobutenes and Bicyclo (2.1.0) Pentanes Through Platinum and Ruthenium- Catalyzed Reactions Zhenjie Ni

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis of Cyclobutenes and Bicyclo (2.1.0) Pentanes Through Platinum and Ruthenium- Catalyzed Reactions Zhenjie Ni Synthesis of Cyclobutenes and Bicyclo (2.1.0) pentanes Through Platinum and Ruthenium- catalyzed Reactions Zhenjie Ni To cite this version: Zhenjie Ni. Synthesis of Cyclobutenes and Bicyclo (2.1.0) pentanes Through Platinum and Ruthenium- catalyzed Reactions. Organic chemistry. Ecole Centrale Marseille, 2014. English. NNT : 2014ECDM0004. tel-01494845 HAL Id: tel-01494845 https://tel.archives-ouvertes.fr/tel-01494845 Submitted on 24 Mar 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. ECOLE CENTRALE MARSEILLE Institut des Sciences Moléculaires de Marseille (UMR 7313) THESE DE DOCTORAT Pour obtenir le garde de: DOCTEUR DE L’ECOLE CENTRALE MARSEILLE Discipline: Sciences Chimiques Ecole Doctotale des Sciences Chimiques ED 250 SYNTHESIS OF CYCLOBUTENES AND BICYCLO[2.1.0]PENTANES THROUGH PLATINUM AND RUTHENIUM-CATALYZED REACTIONS Présentée par Zhenjie NI Directeurs de thèse: Dr. Alphonse TENAGLIA et Dr. Laurent GIORDANO JURY Dr. Elisabet Duñach Université de Nice-Sophia Antipolis Rapporteur Pr. Jean-Marc Campagne Institut Charles Gerhardt, Montpellier Rapporteur Dr. Yves Gimbert Université Joseph Fourier, Grenoble Examinateur Dr. Alphonse Tenaglia Aix-Marseille Université Directeur de thèse Dr. Laurent Giordano Ecole Centrale Marseille Directeur de thèse Acknowledgements First and foremost I would like to extend my deepest gratitude to my thesis advisors, Dr. Alphonse TENAGLIA and Dr. Laurent GIORDANO for the opportunity to work and learn in their laboratories. They devoted a considerable portion of their time for my experiments and my manuscripts. With their assistance and encouragement, I could successfully complete this thesis. From them, I learned much. I would like to thank the members of the committee: Dr. Elisabet Duñach, Pr. Jean-Marc Campagne and Dr. Yves Gimbert for the examination of the contents of the manuscript. I gratefully acknowledges: Dr. Innocenzo DE RIGGI for help with the NMR, Dr. Sabine CHEVALLIER-MICHAUD for help with LC-MS, Dr. Hervé CLAVIER for his helpful suggestions and Dr. David GATINEAU for his kindness. My gratitude also goes to the people in our laboratory: Dr. Damien HERAULT, Pr. Gérard BUONO, Pr. Frédéric FOTIADU, Dr. Julien LECLAIRE, Dr. Didier NUEL, Dr. Delphine MORALEDA, Dr. Guillaume POISSON, Dr. Duc Hanh NGUYEN, Dr. Karel LE-JEUNE, Mr. Pierre-Thomas SKOWRON, Mr. Lionel GRAUX and Mr. Sébastien LEMOUZY. It has been a pleasure to have you as my teachers or friends. I am grateful for the support of my parents, Guihua ZHUANG and Gongquan NI, whom allowed me to pursue my dreams. I would like to thank my girl friend Ran ZHAO, who always supported and encouraged me in the past three years. At last, I gratefully acknowledge the China Scholarship Council (CSC) for the doctoral scholarship. I List of Abbreviations AcOH acetic acid acac acetylacetonate Anal. elemental analysis aq. aqueous BHT Butylated hydroxytoluene BINAP 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl Boc N-tert-butoxycarbonyI Bn benzyl Bz benzoyl br broad (spectroscopy) cat. catalytic calcd calculated cod cyclooctadiene COSY COrrelation spectroScopY Cp cyclopentadienyl Cp* pentamethylcyclopentadienye δ NMR scale d doublet DCE 1,2-dichloroethane DCM dichloromethane DEPT Distortionless Enhancement by Polarization Transfer DIAD diisopropylazodicarboxylate DMA dimethylacetamide DMAD dimethyl acetylenedicarboxylate DMAP 4-dimethylamino pyridine DMF dimethylformamide DMP Dess-Martin periodinane DMPU N,N'-dimethyl-N,N'-propylene urea DMSO dimethylsulfoxide dppe 1,2-diphenylphosphinoethane II EDC·HCl 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride ee enantiomeric excess equiv equivalent h hour HMBC Heteronuclear Multiple Bond Correlation HMQC Heteronuclear Multiple-Quantum Correlation HOBt 1-hydroxybenzotriazole hydrate HPLC High Performance Liquid Chromatography HRMS High Resolution Mass Spectroscopy Hz hertz IR infrared spectroscopy λ wavelength M molarity m multiplet MCPs methylenecyclopropanes MeCN acetonitrile m.p. melting point Ms methanesulfonyl NBS N-bromosuccinimide NMP N-methylpyrrolidone NOESY Nuclear Overhauser Enhancement SpectroscopY PE petroleum ether Rf retention factor value rt room temperature s singlet t triplet TBAF tetra-butylammonium fluoride TBAI tetra-butylammonium iodide TBS tert-butyldimethylsilyl TC thiophene-2-carboxylate TCPC tetracarbomethoxypalladacyclopentadiene Tf trifluoromethanesulfonyl III TFA trifluoroacetic acid THF tetrahydrofuran TIPS triisopropylsilyl TMS trimethylsilyl Ts para-toluenesulfonyl IV Table of Contents General Introduction ················································································································ 1 Chapter I Bibliographic Overview of Transition-Metal Catalyzed Synthesis of Cyclobutenes ····························································································································· 3 Introduction ····························································································································· 4 1.1 Transition-metal Catalyzed Intermolecular [2+2] Cycloadditions of Alkenes and Alknynes ································································································································· 5 1.1.1 Nickel ························································································································· 5 1.1.2 Palladium ···················································································································· 7 1.1.3 Ruthenium ·················································································································· 8 1.1.4 Cobalt ······················································································································· 11 1.1.5 Rhodium ··················································································································· 14 1.1.6 Gold ·························································································································· 15 1.1.7 Silver ························································································································· 16 1.1.8 Rhenium ··················································································································· 17 1.1.9 Iridium ······················································································································ 17 1.1.10 Iron ························································································································· 17 1.1.11 Copper····················································································································· 18 1.2 Transition-metal Catalyzed Intramolecular [2+2] Cycloadditions of Enynes ················ 20 1.2.1 Palladium ·················································································································· 20 1.2.2 Platinum ···················································································································· 21 1.2.3 Gold ·························································································································· 25 1.2.4 Ruthenium ················································································································ 29 1.2.5 Nickel ······················································································································· 32 1.2.6 Gallium ····················································································································· 33 1.2.7 Cobalt ······················································································································· 33 1.3 Transition-metal Catalyzed Intramolecular [2+2] Cycloadditions of Allenynes ············ 34 1.3.1 Platinum ···················································································································· 34 1.3.2 Rhodium ··················································································································· 35 1.3.3 Molybdenum ············································································································· 36 1.4 Cyclobutenes Formation Through Metal-Catalyzed Ring Expansion Reactions ··········· 37 1.4.1 Platinum ···················································································································· 37 1.4.2 Palladium ·················································································································· 38 1.4.3 Silver ························································································································· 39 1.4.4 Rhodium ··················································································································· 40 1.4.5 Gold ·························································································································· 41 1.4.6 Copper ······················································································································
Load more

Recommended publications
  • A-PDF Split DEMO : Purchase from to Remove the Watermark
    A-PDF Split DEMO : Purchase from www.A-PDF.com to remove the watermark Figure 7.5 (a) Transition state for E2H-syn elimination. (b) Transition state for E2H-anti elimination. (c) Transition state for E,C elimination. tion state similar to that shown in Figure 7.5~is expected, since base attacks the molecule backside to the leaving group but frontside to the /3 hydrogen. Let us now turn to the experimental results to see if these predictions are borne out in fact. It has long been known that E2H reactions normally give preferentially anti elimination. For example, reaction of meso-stilbene dibromide with potassium ethoxide gives cis-bromostilbene (Reaction 7.39), whereas reaction of the D,L-dibromide gives the trans product (Reaction 7.40).lo2 A multitude of other examples exist-see, for example, note 64 (p. 355) and note 82 (p. 362). E2H reactions do, however, give syn elimination when: (1) an H-X di- hedral angle of 0" is achievable but one of 180" is not or, put another way, H and X can become syn-periplanar but not trans-periplanar ; (2) a syn hydrogen is much more reactive than the anti ones; (3) syn elimination is favored for steric reasons; and (4) an anionic base that remains coordinated with its cation, that, in turn, is coordinated with the leaving group, is used as catalyst. The very great importance of category 4 has only begun to be fully realized in the early 1970s. lo2 P. Pfeiffer, 2. Physik. Chem. Leibrig, 48, 40 (1904). 1,2-Elimination Reactions 371 An example of category 1 is found in the observation by Brown and Liu that eliminations from the rigid ring system 44, induced by the sodium salt of 2- cyclohexylcyclohexanol in triglyme, produces norborene (98 percent) but no 2-de~teronorbornene.~~~The dihedral angle between D and tosylate is O", but Crown ether present: No Yes that between H and tosylate is 120".
    [Show full text]
  • Nomenclature Cyclic Aliphatic Hydrocarbons Are Named By
    An alicyclic compound is an organic compound that is both aliphatic and cyclic. They contain one or more all-carbon rings which may be either saturated or unsaturated, but do not have aromatic character. Alicyclic compounds may have one or more aliphatic side chains attached. The simplest alicyclic compounds are the 1. monocyclic cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohepta ne, cyclooctane, and so on. 2. Bicyclic alkanes include bicycloundecane, decalin, and housane. 3. Polycyclic alkanes include cubane, basketane, and tetrahedrane. Spiro compounds have two or more rings that are connected through only one carbon atom. Nomenclature Cyclic aliphatic hydrocarbons are named by prefixing cyclo- to the name of the corresponding open-chain hydrocarbon having the same number of carbons as the ring. For example: Cyclopropane Cyclobutane Cyclopentane Cyclopentene Substituents on the ring- alkyl, groups, halogens- are named and their positions indicated by numbers. Chlorocyclopropane 1,1- Dimethylyclopentane 1,3-Dimethylcyclohexane CH3 CH3 Cl H3C CH3 In simple cycloalkenes and cycloalkynes the double and triply bonded carbons are considered to occupy positions 1 and 2. For example: 3-Ethylcyclopentene 1,3-Cyclohexadiene H3C For convenience, aliphatic rings are often represented by simple geometric figures: a triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane, a hexagon for cyclohexane and so on. It is understood that two hydrogens are located at each corner of the figure unless some other group is indicated. For example H3C cyclopentane 3-Ethylcyclopentene 1,3-Cyclopentadiene CH3 CH3 Cl CH Cyclohexane 3 1,3-Dimethylcyclohexane 2- Chloro-1-methylcyclohexane As usual alcohols are given the ending –ol, which takes priority over –ene and appears last in the name.
    [Show full text]
  • New Applications of Cyclobutadiene Cycloadditions: Diversity and Target Oriented Synthesis
    New Applications of Cyclobutadiene Cycloadditions: Diversity and Target Oriented Synthesis Author: Jason Joseph Marineau Persistent link: http://hdl.handle.net/2345/1741 This work is posted on eScholarship@BC, Boston College University Libraries. Boston College Electronic Thesis or Dissertation, 2010 Copyright is held by the author, with all rights reserved, unless otherwise noted. Boston College The Graduate School of Arts and Sciences Department of Chemistry NEW APPLICATIONS OF CYCLOBUTADIENE CYCLOADDITIONS: DIVERSITY AND TARGET ORIENTED SYNTHESIS a dissertation by JASON JOSEPH MARINEAU submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy December 2010 © Copyright by JASON JOSEPH MARINEAU 2010 New Applications of Cyclobutadiene Cycloadditions: Diversity and Target Oriented Synthesis Jason J. Marineau Thesis Advisor: Professor Marc. L. Snapper Abstract Cyclobutadiene cycloadditions provide rapid access to rigid polycyclic systems with high strain energy and unusual molecular geometries. Further functionalization of these systems allows entry into unexplored chemical space. A tricarbonylcyclobutadiene iron complex on solid support enables exploration of these cycloadditions in a parallel format amenable to diversity oriented synthesis. Modeling of the cycloaddition transition states with density functional calculations provides a theoretical basis for analysis of the regioselectivity observed in generation of these substituted bicyclo[2.2.0]hexene derivatives. The high strain energy accessible in cyclobutadiene cycloadducts and their derivatives renders them useful synthons for access to medium-ring natural products through ring expansion. Torilin, a guaiane sesquiterpene isolated from extracts of the fruits of Torilis japonica, exhibits a range of biological activities including testosterone 5 -reductase inhibition, hKv1.5 channel blocking, hepatoprotective, anti-inflammatory and anti-cancer effects.
    [Show full text]
  • Here Science-Based Cost- Effective Pathways Forward?
    Sponsors Institute of Atomic and Molecular Sciences, Academia Sinica, Taiwan PIRE-ECCI Program, UC Santa Barbara, USA Max-Planck-Gesellschaft, Germany National Science Council, Taiwan Organizing committee Dr. Kuei-Hsien Chen (IAMS, Academia Sinica, Taiwan) Dr. Susannah Scott (University of California - Santa Barbara, USA) Dr. Alec Wodtke (University of Göttingen & Max-Planck-Gesellschaft, Germany) Table of Contents General Information .............................................................................................. 1 Program for Sustainable Energy Workshop ....................................................... 3 I01 Dr. Alec M. Wodtke Beam-surface Scattering as a Probe of Chemical Reaction Dynamics at Interfaces ........................................................................................................... 7 I02 Dr. Kopin Liu Imaging the steric effects in polyatomic reactions ............................................. 9 I03 Dr. Chi-Kung Ni Energy Transfer of Highly Vibrationally Excited Molecules and Supercollisions ................................................................................................. 11 I04 Dr. Eckart Hasselbrink Energy Conversion from Catalytic Reactions to Hot Electrons in Thin Metal Heterostructures ............................................................................................... 13 I05 Dr. Jim Jr-Min Lin ClOOCl and Ozone Hole — A Catalytic Cycle that We Don’t Like ............... 15 I06 Dr. Trevor W. Hayton Nitric Oxide Reduction Mediated by a Nickel Complex
    [Show full text]
  • The X1 Method for Accurate and Efficient Prediction of Heats of Formation
    THE JOURNAL OF CHEMICAL PHYSICS 127, 214105 ͑2007͒ The X1 method for accurate and efficient prediction of heats of formation ͒ Jianming Wu and Xin Xua State Key Laboratory of Physical Chemistry of Solid Surfaces and Center for Theoretical Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China ͑Received 31 July 2007; accepted 25 September 2007; published online 5 December 2007͒ We propose the X1 method which combines the density functional theory method with a neural network ͑NN͒ correction for an accurate yet efficient prediction of heats of formation. It calculates the final energy by using B3LYP/6-311+G͑3df,2p͒ at the B3LYP/6-311+G͑d,p͒ optimized geometry to obtain the B3LYP standard heats of formation at 298 K with the unscaled zero-point energy and thermal corrections at the latter basis set. The NN parameters cover 15 elements of H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, and Cl. The performance of X1 is close to the Gn theories, giving a mean absolute deviation of 1.43 kcal/mol for the G3/99 set of 223 molecules up to 10 nonhydrogen atoms and 1.48 kcal/mol for the X1/07 set of 393 molecules up to 32 nonhydrogen atoms. © 2007 American Institute of Physics. ͓DOI: 10.1063/1.2800018͔ I. INTRODUCTION the B3LYP method to calculate heats of formation of neutral organic molecules. Their results are promising. Calibrated ͑⌬ ␪͒ The accurate prediction of heats of formation Hf is with their own compilation of 180 organic molecules for the one of the central topics in computational chemistry.
    [Show full text]
  • Cucurbiturils: from Synthesis to High-Affinity Binding and Catalysis
    Chemical Society Reviews Cucurbiturils: From Synthesis to High -Affinity Binding and Catalysis Journal: Chemical Society Reviews Manuscript ID: CS-REV-08-2014-000273.R1 Article Type: Review Article Date Submitted by the Author: 24-Sep-2014 Complete List of Authors: Nau, Werner; Jacobs University, School of Engineering and Science Assaf, Khaleel; Jacobs University Bremen, Page 1 of 49 Chemical Society Reviews Table of contents entry Major developments in the synthesis of cucurbiturils and applications related to their high-affinity binding and catalysis have recently taken place. Chemical Society Reviews Page 2 of 49 Cucurbiturils: From Synthesis to High-Affinity Binding and Catalysis Khaleel I. Assaf and Werner M. Nau Jacobs University Bremen, Campus Ring 1, 28759 Bremen, Germany 1 Page 3 of 49 Chemical Society Reviews Cucurbiturils: From Synthesis to High-Affinity Binding and Catalysis Khaleel I. Assaf and Werner M. Nau Jacobs University Bremen, Campus Ring 1, 28759 Bremen, Germany Abstract. In the wide area of supramolecular chemistry, cucurbit[n]urils (CB n) present themselves as a young family of molecular containers, able to form stable complexes with various guests, including drug molecules, amino acids and peptides, saccharides, dyes, hydrocarbons, perfluorinated hydrocarbons, and even high molecular weight guests such as proteins ( e.g. , human insulin). Since the discovery of the first CBn, CB6, the field has seen tremendous growth with respect to the synthesis of new homologues and derivatives, the discovery of record binding affinities of guest molecules in their hydrophobic cavity, and associated applications ranging from sensing to drug delivery. In this review, we discuss in detail the fundamental properties of CB n homologues and their cyclic derivatives with a focus on their synthesis and their applications in catalysis.
    [Show full text]
  • Host-Guest Complexes of Cucurbit[7]Uril with Cationic Drugs
    HOST-GUEST COMPLEXES OF CUCURBIT[7]URIL WITH CATIONIC DRUGS AND AMINO ACID DERIVATIVES by Mona A. Gamal-Eldin A thesis submitted to the Department of Chemistry In conformity with the requirements for the degree of Doctor of Philosophy Queen’s University Kingston, Ontario, Canada September 2013 Copyright © Mona A. Gamal-Eldin, 2013 Abstract The host-guest chemistry between cucurbit[7]uril (CB[7]) and cationic organic guests of medicinal and biological interest are described in this thesis. In the first part, three cationic steroidal neuromuscular blockers (SNMBs) were studied, along with guests that model their monocationic N-alkyl-N-methylheterocyclic (morpholinium, pyrrolidinium and piperidinium) terminal groups of the SNMBs, and dicationic guests in which the two N-methylheterocyclic rings are linked by a decamethylene chain, modelling a variety of NMBs. Other cationic drugs related to acetylcholine processes in neuromuscular blockage were also studied. In the second part, the amino acids lysine, and its mono-, di- and trimethylated and acetylated N derivatives, and arginine, and mono- and (symmetric and asymmetric) dimethylarginine, were investigated as guests, along with analogs of arginine. The nature and strength of the complexation between CB[7] and these guests in aqueous solution were determined by 1H NMR spectroscopy and ESI mass spectrometry. 6 9 -1 The CB[7] showed high binding affinity (KCB[7] = 10 -10 M ) towards the N-alkyl-N- methylheterocyclic cations with a trend of piperidinium > pyrrolidinium > morpholinium, which reflects the relative hydrophobicities of the guests. The CB[7] forms 1:1 and 2:1 host-guest complexes with dicationic model guests, with the CB[7] initially encapsulating the decamethylene chain.
    [Show full text]
  • Chem 51A Chapter 4 2014
    Lecture Notes Chem 51A S. King Chapter 4 Alkanes I. Alkanes – An Introduction Alkanes are aliphatic hydrocarbons having only C−H and C−C σ-bonds. They can be cyclic or acyclic. • Acyclic alkanes have the molecular formula CnH2n+2 (where n = an integer.) They are also called saturated hydrocarbons because they have the maximum number of hydrogen atoms per carbon. • Cyclic alkanes contain carbon atoms joined into a ring. They have molecular formula CnH2n. (Notice: 2 less hydrogens than saturated alkanes – Why? A. Unbranched Alkanes Alkanes with unbranched carbon chains are also known as normal alkanes or n- alkanes. The first four n-alkanes: H H H H H H H H H H H C H H C C H H C C C H H C C C C H H H H H H H H H H H • This is an example of a family of compounds known as homologous series (each member differs from the next by the addition of one methylene group (CH2). The first 12 n-alkanes are listed in the handout Essential Nomenclature. 71 Look at the various representations of propane: H H H H H H H C3H8 CH3CH2CH3 H C C C H C C H C H H H H H H H CH 3 H CH3 C H H H CH3 H H B. Branched Alkanes As the number of carbons of an alkane increase beyond three, the number of possible structures increases. An alkane with molecular formula C4H10, for example has two different ways to connect atoms together: CH3 CH2 CH2 CH3 CH3 CH CH3 CH3 These are examples of constitutional isomers: Compounds that have the same molecular formula but different connectivity.
    [Show full text]
  • Chem 260 Handout 2013 Hydrocarbons
    Hydrocarbons — Compounds that contain only Carbon and Hydrogen Types of hydrocarbons: Saturated: Alkanes only single, covalent C-C and C-H bonds, no rings Cycloalkanes same, but contain rings Unsaturated: Alkenes contain > 1 C=C double bond Alkynes contain > 1 C≡C triple bond Aromatic contain > 1 benzene ring General formula for alkanes is: CnH2n+2, n = 1, 2, 3 ... All carbons in alkanes are sp3 hybridized and tetrahedral (bond angles are 109.5°). The suffix "-ane" denotes an alkane. Be familiar with the variety of types of drawings of organic molecules. Know what atom is bonded to what atom. Dashes/wedges: recall that dashed bonds are going into the page, wedged bonds are coming out of the page, and lines are in the plane of the page. Line drawings: Each intersection or end of a line represents a carbon with the correct number of hydrogen atoms. Carbon always has four bonds in stable species. Hydrogens are often not drawn: be sure you know how many hydrogens are on each carbon: draw them in each time if it helps you. Be familiar with the following nomenclature: n = 1 methane n = 5 pentane n = 8 octane n = 2 ethane n = 6 hexane n = 9 nonane n = 3 propane n = 7 heptane n = 10 decane n = 4 butane Interlude: What do we have to know? Will this be on the exam? Anything could appear on an exam. But you should focus on what you really need to know. Know the drawings and nomenclature (don’t bother with index cards, most nomenclature comes just be doing homework).
    [Show full text]
  • Cucurbiturils: from Synthesis to High-Affinity Binding and Catalysis
    Volume 44 Number 2 21 January 2015 Pages 385–604 Chem Soc Rev Chemical Society Reviews www.rsc.org/chemsocrev Themed issue: Molecular containers ISSN 0306-0012 REVIEW ARTICLE Khaleel I. Assaf and Werner M. Nau Cucurbiturils: from synthesis to high-affi nity binding and catalysis Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Cucurbiturils: from synthesis to high-affinity binding and catalysis Cite this: Chem. Soc. Rev., 2015, 44,394 Khaleel I. Assaf and Werner M. Nau* In the wide area of supramolecular chemistry, cucurbit[n]urils (CBn) present themselves as a young family of molecular containers, able to form stable complexes with various guests, including drug molecules, amino acids and peptides, saccharides, dyes, hydrocarbons, perfluorinatedhydrocarbons,andevenhighmolecular weight guests such as proteins (e.g., human insulin). Since the discovery of the first CBn, CB6, the field has Received 9th August 2014 seen tremendous growth with respect to the synthesis of new homologues and derivatives, the discovery of DOI: 10.1039/c4cs00273c record binding affinities of guest molecules in their hydrophobic cavity, and associated applications ranging from sensing to drug delivery. In this review, we discuss in detail the fundamental properties of CBn www.rsc.org/csr homologues and their cyclic derivatives with a focus on their synthesis and their applications in catalysis. Creative Commons Attribution 3.0 Unported Licence. 1. Introduction different perspectives.1–7 Most recently, the synthesis of func- tionalized derivatives has progressed, and among the manifold The chemistry of cucurbit[n]urils (CBn)isarapidlydevelop- applications, cucurbituril-catalyzed reactions are receiving ing field (Fig.
    [Show full text]
  • Modeling the Heat of Formation of Organic Compounds Using SPARC
    Modeling the Heat of Formation of Organic Compounds Using SPARC by Tad S. Whiteside (Under the direction of Lionel Carreira) Abstract Typically, the interaction of chemicals with the environment is governed through physic- ochemical properties. The Environmental Protection Agency has developed several models to predict the fate of chemicals in the environment. SPARC (SPARC Performs Automated Reasoning in Chemistry) has been developed as a method to predict the properties of envi- ronmentally sensitive compounds. SPARC uses computational algorithms based on chemical structure theory to calculate chemical properties, including the heat of formation. Molecular structures are broken into simple functional units (reactophores) with intrinsic properties. Each reactophore is analyzed and the effects of appended molecular structures are quantified through perturbation theory. Standard enthalpies of formation (∆Hf ) were calculated with models developed using the computer program SPARC. The ∆Hf models have been completely developed using all known data for saturated and unsaturated hydrocarbons and halogenated hydrocarbons. Basic models have also been developed for alcohols, aldehydes, and ketones. The structures of these compounds vary from chains and conjugated rings to poly-benzoic aromatic hydro- carbons. The 587 hydrocarbons have a SPARC calculated RMS of 4.50 kJ mol-1. Halogenated hydrocarbons have a calculated RMS deviation of 5.18 kJ mol-1 for 202 compounds. The effect of stereochemistry on the standard enthalpy of formation was also modeled. Chiral centers are found in a variety of molecules and help define the overall structure of a compound. The local atomic environment determines the strain energy in each chiral center. There are four local environments in which chiral centers are found: Linear, Single, Bridge, and SideShare.
    [Show full text]
  • Development of Palladium-Catalyzed Decarboxylative Benzylation Reactions
    Syntheses of Functionalized Benzylic Compounds: Development of Palladium-catalyzed Decarboxylative Benzylation Reactions by Robert Ryan Pangilinan Torregrosa B.S. Chemistry, University of Santo Tomas, Manila Philippines, 2005 Submitted to the Department of Chemistry and the Faculty of the Graduate School of The University of Kansas in partial fulfillment of the requirements for the degree of Doctor of Philosophy _______________________________ Jon A. Tunge, chairperson _______________________________ Paul R. Hanson _______________________________ Richard S. Givens _______________________________ David R. Benson _______________________________ Apurba Dutta Date Defended: July 24, 2012 The Dissertation Committee for Robert Ryan Pangilinan Torregrosa certifies that this is the approved version of the following dissertation: Syntheses of Functionalized Benzylic Compounds: Development of Palladium-catalyzed Decarboxylative Benzylation Reactions _______________________________ Jon A. Tunge, chairperson _______________________________ Paul R. Hanson _______________________________ Richard S. Givens _______________________________ David R. Benson _______________________________ Apurba Dutta Date Defended: July 24, 2012 ii Abstract Robert R. P. Torregrosa Department of Chemistry, July 2012 The University of Kansas Carbon-carbon bond formation between the benzyl carbon and a functional group is important in organic synthesis because majority of the compounds in the chemical literature contain aromatic cores appended with different functionalities
    [Show full text]