DOCSLIB.ORG

Application of Coordination Compounds with Transition Metal Ions in the Chemical Industry—A Review

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Application of Coordination Compounds with Transition Metal Ions in the Chemical Industry—A Review International Journal of Molecular Sciences Review Application of Coordination Compounds with Transition Metal Ions in the Chemical Industry—A Review Jacek Malinowski 1 , Dominika Zych 1, Dagmara Jacewicz 1, Barbara Gawdzik 2,* and Joanna Drze˙zd˙zon 1 1 Faculty of Chemistry, University of Gda´nsk,Wita Stwosza 63, 80-308 Gda´nsk,Poland; [email protected] (J.M.); [email protected] (D.Z.); [email protected] (D.J.); [email protected] (J.D.) 2 Institute of Chemistry, Jan Kochanowski University, Swi˛etokrzyska15´ G, 25-406 Kielce, Poland * Correspondence: [email protected]; Tel.: +48-41-349-70-16 Received: 4 July 2020; Accepted: 27 July 2020; Published: 30 July 2020 Abstract: This publication presents the new trends and opportunities for further development of coordination compounds used in the chemical industry. The review describes the influence of various physicochemical factors regarding the coordination relationship (for example, steric hindrance, electron density, complex geometry, ligand), which condition technological processes. Coordination compounds are catalysts in technological processes used during organic synthesis, for example: Oxidation reactions, hydroformylation process, hydrogenation reaction, hydrocyanation process. In this article, we pointed out the possibilities of using complex compounds in catalysis, and we noticed what further research should be undertaken for this purpose. Keywords: coordination compounds; chemical industry; polymer materials; technological processes 1. Introduction The use of complex compounds in processes employed in the broadly understood chemical industry is a very important aspect of the work of scientists around the world. Processes carried out on an industrial scale and conducted by scientists are enjoying the growing recognition of global corporations dealing in the production of various polymeric materials used in many aspects of our lives [1–4]. In order to understand the important function of coordination compounds in catalytic reactions during industrial processes carried out on an industrial scale, it is necessary to learn the exact mechanisms of the reactions carried out. Delving into the mechanism of an exemplary process will allow us to conclude that the most important changes occur in the coordination sphere of the comprehensive relationship. This means that many factors related to geometry, steric hindrance, or the used central atom and attached ligands of the complex compound affect the catalytic reaction. In recent years, the focus has been on improving the efficiency and selectivity of processes. It has been confirmed that the selection of appropriate ligands in the metal coordination sphere allows a catalyst with properties that have been planned to be obtained. We can therefore conclude that the catalytic properties of the complex compound used depend to the greatest extent on the structure of the catalyst [5,6]. A very important aspect of work on chemical technologies is the smallest possible pollution of the environment, i.e., the application of the principles of green chemistry. Conducting reactions in organic solvents is replaced by supercritical liquids or ionic liquids. Developing the implement of Int. J. Mol. Sci. 2020, 21, 5443; doi:10.3390/ijms21155443 www.mdpi.com/journal/ijms Int. J. Mol. Sci. 2020, 21, x FOR PEER REVIEW 2 of 26 Int. J. Mol. Sci. 2020, 21, 5443 2 of 26 organic solvents is replaced by supercritical liquids or ionic liquids. Developing the implement of biotechnological andand organocatalytic organocatalytic methods methods allows environmentallyallows environmentally friendly chemical friendly technologies chemical technologiesto be obtained to [ 7be,8 ].obtained [7,8]. In this publication, we present the latest methods of using coordination compounds in catalytic reactions used used in in the the chemical chemical indus industry.try. We We present present the the influence influence of coordination of coordination compounds compounds on the on coursethe course of reactions of reactions taking taking place place in inorganic organic synthesis synthesis (for (for example: example: H Hydroformylationydroformylation process, process, hydrogenation reaction, oxidation processes, olefin olefin polymerization processes). We We also describe the application of green chemistry principles in a catalysis catalysis with with the the participation participation of of complex complex compounds. compounds. 2. Oxidation Oxidation P Processesrocesses 2.1. Wacker Wacker P Processrocess The Wacker processprocess was was developed developed in in cooperation cooperation of twoof two concerns, concerns, Wacker Wacker and and Hoechst, Hoechst, and thenand publishedthen published in 1959. in 195 The9. The process process is ais well-knowna well-known reaction reaction for for obtaining obtaining acetaldehyde acetaldehyde byby oxidation of ethene. ethene. The The reaction reaction is carried is carried out outin an in aqueous an aqueous environment environment usingusing a homogeneous a homogeneous catalyst catalyst (PdCl2 (PdCl CuCl ). The synthesis was recognized by the chemical industry, due to the fact that it was an · CuCl22·). The 2synthesis was recognized by the chemical industry, due to the fact that it was an alternative to the hydroformylation reaction. The The acetaldehyde acetaldehyde obtained obtained in in the the synthesis is widely used. It It is is mainly applied for production of acetic acid, acetic anhydride or chloroform. In In addition, addition, it can form syntheticsynthetic resinsresins inin condensationcondensation reactions reactions with with phenols phenols and and amines. amines. The The Wacker Wacker process process is isshown shown in Figurein Figure1, in 1, which in which stoichiometric stoichiometric reactions reactions combine combine in one in catalytic one catalytic cycle. cycle. In the In first the stage, first stage,in an aqueousin an aqueous environment, environment, it reacts it with reacts palladium(II) with palladium( chloride,II) formingchloride, a forming stoichiometric a stoichiometric amount of amountacetaldehyde, of acetaldehyde, and palladium(II) and palladium(II) is reduced tois reduced palladium(0). to palladium(0). In the next In stage, the next palladium(0) stage, palladium(0) undergoes undergoesreoxidation reoxidation in the presence in the ofpresence copper(II) of copper(II) compounds. compounds. Copper(I) Copper(I) is formed is formed as the product as the product of this ofreaction this reaction while in while the last in the stage last copper(I) stage copper(I) is oxidized is oxidized with oxygen with tooxygen copper(II). to copper(II). Reaction Reaction 4 in Figure 4 in1 Figurerepresents 1 represents the overall the reaction overall ofreaction the process of the [ 9process,10]. [9,10]. Figure 1. ReactionsReactions forming forming the the catalytic catalytic cycle of the Wacker process [11].]. 2 According to research recommendations, thethe oxidationoxidation stagestage isis actuallyactually catalyzedcatalyzed byby [PdCl[PdCl44]]2−−,, which is formed underunder thethe conditionsconditions ofof waterwater andand ClCl−− ions.ions. In In the the analyzed cycle, two chloride ligands are replaced by ethene and water. In the next stage, there is a nucleophilic attack of water on ethene in in the the complex, complex, followed followed by by substitution substitution of of the the chloride chloride ligand ligand by byanother another water water molecule. molecule. β- eliminationβ-elimination of ofa hydrogen a hydrogen atom atom leads leads to tothe the formation formation of ofvinyl vinyl alcohol. alcohol. This This stage stage is isfollowed followed by by a seriesa series of ofpro processescesses leading leading to tothe the production production of ofacetaldehyde acetaldehyde and and palladium(II) palladium(II) hydride. hydride. Due Due to the to factthe factthat that palladium(II) palladium(II) hydride hydride is unstable, is unstable, Pd(0) Pd(0) and and HCl HCl are are formed formed as as a aresult result of of the the reduction reaction. The The cycle cycle is closed. Palladium(0) Palladium(0) is is oxidized oxidized to to palladium(I palladium(II)I) with CuCl 2 [11,12].[11,12]. Int. J. Mol. Sci. 2020, 21, 5443 3 of 26 In [13] the researchers carried out quantum mechanical tests and they concluded that the anti-nucleophilic attack is the step determining the Wacker process under standard conditions. Unfortunately, experimental studies did not confirm the results obtained by calculation methods. Keith et al. report that the Wacker process is determined by a syn-nucleophilic attack [14]. The Wacker oxidation usually gives ketones as reaction products, but the literature reports that one can carry out the Wacker process that will give 99% selectivity in obtaining aldehydes, e.g., using 1,4-benzoquinone, t-BuOH, and PdCl2 (MeCN)2 [15–18]. Regarding the selectivity of the Wacker process, products with high selectivity are also obtained using styrene derivatives as substrates with the reaction carried out under mild conditions [19]. Studies conducted over the years proved that the Wacker process produces environmentally hazardous, chlorinated by-products, as well as harmful copper waste. According to the principles of green chemistry, solutions are being sought that affect the protection of ecosystems and the whole world. Researchers at the University of Pune proposed the Pd(0)/C system as a heterogeneous catalyst that can be recycled. This allowed the elimination of pure
Load more

Recommended publications
  • Mechanistic Insights Into the Hydrocyanation Reaction
    Mechanistic insights into the hydrocyanation reaction Citation for published version (APA): Bini, L. (2009). Mechanistic insights into the hydrocyanation reaction. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR644067 DOI: 10.6100/IR644067 Document status and date: Published: 01/01/2009 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal.
    [Show full text]
  • Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)**
    NOBEL LECTURES DOI: 10.1002/adsc.200600523 Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)** Robert H. Grubbsa,* a Victor and Elizabeth Atkins Professor of Chemistry Arnold and Mabel Beckman Laboratories of Chemical Synthesis California Institute of Technology, Pasadena, CA 91125, USA Fax : (+1)-626–564–9297 [**] Copyright The Nobel Foundation 2005. We thank the Nobel Foundation, Stockholm, for permission to print this lecture Received: February 21, 2006 This is a story of our exploration of the olefin-meta- ly added to this reaction, 1-butene was again ob- thesis reaction, a reaction that has been the major served. This discovery has since served as the founda- emphasis of my independent research. As with all sto- tion for an amazing array of nickel chemistry and cat- ries of scientific discovery, there are three compo- alysis. In addition, as nickel had been found to possess nents: the discoveries, the resulting applications, and, unexpected reactivity, other metal salts were also in- perhaps the most important of all, the people in- vestigated. In particular, when titanium and zirconium volved. Starting from observations made from seem- halides were used in combination with alkyl alumi- ingly unrelated work, our investigations into the fun- num compounds, a new form of polyethylene was ob- damental chemistry of this transformation have been tained. Natta further demonstrated that similar cata- an exciting journey, with major advances often result- lysts could promote the formation of stereoregular ing from complete surprises, mistakes, and simple in- polymers from propylene. The 1963 Nobel Prize in tuition. Ultimately, these efforts have contributed to Chemistry was awarded to Ziegler and Natta for this olefin metathesis becoming the indispensable synthet- work.
    [Show full text]
  • Part I: Carbonyl-Olefin Metathesis of Norbornene
    Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis…………………………………………………………….
    [Show full text]
  • Bimetallic Catalyst Catalyzed Carbonylation of Methanol to Acetic Acid
    materials Article Study on Rh(I)/Ru(III) Bimetallic Catalyst Catalyzed Carbonylation of Methanol to Acetic Acid Shasha Zhang 1, Wenxin Ji 1,2,*, Ning Feng 2, Liping Lan 1, Yuanyuan Li 1,2 and Yulong Ma 1,2 1 College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China; [email protected] (S.Z.); [email protected] (L.L.); [email protected] (Y.L.); [email protected] (Y.M.) 2 State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China; [email protected] * Correspondence: [email protected]; Tel.: +86-135-1957-9989; Fax: +86-951-206-2323 Received: 13 July 2020; Accepted: 3 September 2020; Published: 11 September 2020 Abstract: In this study, a Rh(I)/Ru(III) catalyst with a bimetallic space structure was designed and synthesized. The interaction between the metals of the bimetallic catalyst and the structure of the bridged dimer can effectively reduce the steric hindrance effect and help speed up the reaction rate while ensuring the stability of the catalyst. X-ray photoelectron spectroscopy (XPS) results show that rhodium accepts electrons from chlorine, thereby increasing the electron-rich nature of rhodium and improving the catalytic activity. This promotes the nucleophilic reaction of the catalyst with methyl iodide and reduces the reaction energy barrier. The methanol carbonylation performance of the Rh/Ru catalyst was evaluated, and the results show that the conversion rate of methyl acetate and the yield of acetic acid are 96.0% under certain conditions. Furthermore, during the catalysis, no precipitate is formed and the amount of water is greatly reduced.
    [Show full text]
  • 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.
    [Show full text]
  • Self-Metathesis of 1-Octene Using Alumina-Supported Re2o7 in Supercritical CO2
    Top Catal DOI 10.1007/s11244-008-9154-4 ORIGINAL PAPER Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2 Massimo Fabris Æ Cindy Aquino Æ Antony J. Ward Æ Alvise Perosa Æ Thomas Maschmeyer Æ Maurizio Selva Ó Springer Science+Business Media, LLC 2009 Abstract In this contribution we describe the use of basic science has been applied for the benefit of man, heterogeneous catalysts for the liquid-phase self-metathesis society and the environment’’.1 Their contribution was of 1-octene in supercritical CO2. Our work aims at recognized for understanding the mechanism, and for addressing the mass-transfer problems associated with such developing very efficient and selective discrete metal- reaction systems. By coupling a heterogeneous supported based catalysts. Re2O7 catalyst with the use of scCO2, the self-metathesis Nonetheless, one should not forget that the metathesis of 1-octene takes place by and large much more rapidly reaction using heterogeneous catalysis has been an estab- than in traditional solvent media, and furthermore, by using lished industrial process since 1966, based on the use of scCO2 the overall efficiency and sustainability of the supported (usually on silica and alumina) metal oxides transformation can be improved. such as tungsten, nickel, cobalt, rhenium, and molybde- num. Three significant examples come to mind and are Keywords Metathesis Á 1-Octene Á Supercritical CO2 Á here recalled briefly. [1]. Re/Al O 2 3 1. The historic Phillips triolefin process for the produc- tion of ethene and 2-butene from propene using a WO /SiO catalyst, [2] that was shut down in 1972 1 Introduction 3 2 after 6 years of operation due to increased demand for propene, and later reutilized in the reverse direction to The metathesis of olefins is a very elegant and widely produce propene.
    [Show full text]
  • CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R
    CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R. Petersen†, Ji-Woong Lee*,† †Department of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark KEYWORDS: Carbon Dioxide, Cyanohydrin, Xanthate, Homologation ABSTRACT: Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protect- ing groups. Here we report the use of carbon dioxide to direct reaction pathways in order to selectively afford desired products in high reaction rates while avoiding the formation of byproducts. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani-Fischer synthesis to offer an easy access to variety of polyols, cyanohydrins, linear al- kylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and atmospheric pressure of CO2. 9 A chemical reaction is governed by kinetics and ther- investigated the role of CO2 in a cyanation reaction, where CO2 modynamics, and a simultaneous control of both parameters is can be used in catalytic amounts to facilitate the stereoselective a common practice in designing and optimizing chemical reac- transformation of activated electrophiles via 1,4-conjugate ad- tions. The manipulation of thermodynamic stability of reactants dition reactions. Cyanohydrin synthesis - 1,2-cyanide addition and products
    [Show full text]
  • 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.
    [Show full text]
  • Organometallic and Catalysis
    ORGANOMETALLIC AND CATALYSIS Dr. Malay Dolai, Assistant Professor, Department of Chemistry, Prabhat Kumar College, Contai, Purba Medinipur-721404, WB, India. 1.Introduction Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and tin, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. In 1827, Zeise's salt is the first platinum- olefin complex: K[PtCl3(C2H4)].H2O, the first invented organometallic compound. Organometallic compounds find wide use in commercial reactions, both as homogeneous catalysis and as stoichiometric reagents For instance, organolithium, organomagnesium, and organoaluminium compounds, examples of which are highly basic and highly reducing, are useful stoichiometrically, but also catalyze many polymerization reactions. Almost all processes involving carbon monoxide rely on catalysts, notable examples being described as carbonylations. The production of acetic acid from methanol and carbon monoxide is catalyzed via metal carbonyl complexes in the Monsanto process and Cativa process. Most synthetic aldehydes are produced via hydroformylation. The bulk of the synthetic alcohols, at least those larger than ethanol, are produced by hydrogenation of hydroformylation- derived aldehydes.
    [Show full text]
  • Introduction
    1 Chapter 1 INTRODUCTION Significant research efforts in the field of transition metal catalysis have led to the development of powerful methods for the formation of C–C and C–heteroatom bonds. Appropriate design of the catalyst and reaction conditions, along with careful choice of the substrate, can enable new and challenging transformations to proceed in high yield and selectivity. In this thesis, three categories of such transformations are presented: cross- coupling reactions to form carbon–silicon bonds, aldehyde-selective Wacker oxidations of fluorinated olefins, and olefin metathesis catalyzed by aminophosphine-ligated ruthenium complexes. Nickel-catalyzed cross-coupling has proven to be a very effective strategy for the addition of organometallic reagents to unactivated alkyl electrophiles. In particular, secondary alkyl halides are useful coupling partners, despite previously being considered to exhibit poor reactivity in comparison to aryl and alkenyl electrophiles, due to challenging oxidative addition and competitive b-hydride elimination. While this class of reactions has predominantly been applied to the formation of C–C bonds, the extension of this strategy to the formation of C–B bonds presented by Fu and coworkers inspired the work presented in the second chapter of this thesis, which details the development of a nickel-catalyzed cross- coupling reaction of unactivated alkyl bromides and silylzinc nucleophiles, resulting in C–Si bond formation. A brief overview of established strategies to form C–Si bonds, as well as some of the current challenges, is discussed. The palladium-catalyzed Wacker oxidation is a powerful tool for the oxidation of terminal olefins. However, controlling the regioselectivity of this process (i.e.
    [Show full text]
  • 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.
    [Show full text]
  • 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.
    [Show full text]