DOCSLIB.ORG

Amines in Olefin Metathesis: Ligands and Poisons

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Amines in Olefin Metathesis: Ligands and Poisons Amines in Olefin Metathesis: Ligands and Poisons Benjamin John Ireland A thesis submitted to the Faculty of Graduate and Postdoctoral Studies in partial fulfillment of the requirements for the degree of Doctor of Philosophy Ottawa-Carleton Chemistry Institute Faculty of Science University of Ottawa © Benjamin J. Ireland, Ottawa, Canada 2016 Table of Contents Abstract ............................................................................................................................................... IV Acknowledgements .............................................................................................................................. V Lists of Compounds and Abbreviations ........................................................................................... VI Lists of Charts, Schemes, Figures, and Tables .............................................................................. XIV Chapter 1. Introduction ......................................................................................................................... 1 1.1. Catalysis ...................................................................................................................................... 1 1.2. Olefin metathesis ......................................................................................................................... 2 1.2.1. A powerful tool for organic synthesis .................................................................................. 2 1.2.2. The history and mechanism of olefin metathesis - highlights .............................................. 5 1.2.3. Well-defined metal alkylidenes as metathesis catalysts ....................................................... 7 1.2.4. Non-productive metathesis reactions ................................................................................. 11 1.3. Catalyst decomposition pathways ............................................................................................. 13 1.3.1. Inherent decomposition of Ru-alkylidenes and MCB complexes ....................................... 13 1.3.2. Decomposition induced by chemical additives .................................................................. 14 1.4. Amines in catalyst design - opportunities .................................................................................. 17 1.5. Scope of thesis ........................................................................................................................... 18 Chapter 2. Experimental Details ......................................................................................................... 23 2.1. General procedures ................................................................................................................... 23 2.1.1. Reaction conditions ............................................................................................................ 23 2.1.2. Reagents and solvents ........................................................................................................ 23 2.1.3. Instrumentation .................................................................................................................. 24 2.1.4. Supplementary data ............................................................................................................ 25 2.2. Experimental data for Chapter 3 ............................................................................................... 25 2.2.1. Stoichiometric reactions of GI, GII, and GII’ with N-donors ............................................ 25 2.2.2. Syntheses of new compounds ............................................................................................. 26 2.2.3. Characterization data for benzylidene abstraction products ............................................ 27 2.3. Experimental data for Chapter 4 ............................................................................................... 28 2.3.1. Experimental details for Chapter 4, Sections 4.1-4.3 ........................................................ 28 2.3.2. Experimental details for Chapter 4, Section 4.4. ............................................................... 32 2.4. Experimental data for Chapter 5 ............................................................................................... 33 2.4.1. Syntheses of GII adducts of pyrroldine and morpholine (Section 5.2.1) ........................... 33 2.4.2. Syntheses of other new Ru benzylidenes ............................................................................ 34 2.4.3. Olefin metathesis ................................................................................................................ 37 2.4.2. Decomposition studies ....................................................................................................... 37 2.4.3. Reactions of Ru alkylidenes with lithium salts ................................................................... 39 2.4.4. Experimental details for Chapter 5, Section 5.6 ................................................................ 40 2.6. References ................................................................................................................................. 44 Chapter 3. Decomposition of the Grubbs Catalysts by Amines: Benzylidene Abstraction ............... 46 3.1. Introduction ............................................................................................................................... 46 3.2. Decomposition of the first-generation Grubbs catalyst GI by benzylidene abstraction ........... 50 3.2.1. Unexpected abstraction of the benzylidene ligand from GI by n-butylamine .................... 50 3.2.2. Benzylidene abstraction from an ethylenediamine (en) derivative of GI .......................... 53 3.3. Reactions of GII with primary amines ...................................................................................... 54 3.3.1. Benzylidene abstraction by n-butylamine: identification of products ............................... 54 3.3.2. Benzylidene abstraction from amine adducts of GII as compared with GII ...................... 57 3.3.3. Reactions of GII with larger primary amines .................................................................... 58 II 3.3.4. Proposed mechanism for benzylidene abstraction by primary amines .............................. 60 3.4. Reactions of GII with secondary amines and larger N-donors ................................................. 62 3.5. Conclusions and future work ..................................................................................................... 63 3.6. References ................................................................................................................................. 64 Chapter 4. The Impact of Nitrogen Bases on the Stability and Metathesis Performance of the Hoveyda Catalyst: Alkylidene and Proton Abstraction Pathways ....................................................... 66 4.1. Introduction ............................................................................................................................... 66 4.2. Adduct formation on reaction of HII with N-donors ................................................................. 68 4.3. Base-induced decomposition of HII and its active species during metathesis .......................... 73 4.4. Subsequent advances ................................................................................................................. 79 4.4.1. C–H activation of the N-heterocyclic carbene during metallacyclobutane decomposition ...................................................................................................................................................... 79 4.4.2. Can GII decompose via deprotonation of the metallacyclobutane? .................................. 82 4.4.3. Impact of N-donors on CM yield: GII vs. HII .................................................................... 82 4.4.4. The role of amine basicity in determining the decomposition pathway for GII ................ 84 4.4.5. Metallacyclobutane deprotonation with GII – ethenolysis ................................................ 85 4.4.6. Alkylidene abstraction from HII during catalysis .............................................................. 86 4.5. Conclusions and future work ..................................................................................................... 90 4.6. References ................................................................................................................................. 92 Chapter 5. Amines as Ligands in Olefin Metathesis ........................................................................... 95 5.1. Nitrogen ligands in olefin metathesis – design opportunities ................................................... 95 5.2. Synthesis of Ru benzylidenes with amine ligands ...................................................................... 97 5.2.1. Synthesis and characterization of Grubbs benzylidenes with monodentate amine ligands ...................................................................................................................................................... 97 5.2.2. Synthesis and characterization of benzylidene complexes with chelating diamines. ........ 99 5.3. Olefin metathesis studies with biphenylamine catalysts .......................................................... 104 5.4. Decomposition studies of biphenyldiamine derivatives .........................................................
Load more

Recommended publications
  • Significance and Implications of Vitamin B-12 Reaction Shema- ETH ZURICH VARIANT: Mechanisms and Insights
    Taylor University Pillars at Taylor University Student Scholarship: Chemistry Chemistry and Biochemistry Fall 2019 Significance and Implications of Vitamin B-12 Reaction Shema- ETH ZURICH VARIANT: Mechanisms and Insights David Joshua Ferguson Follow this and additional works at: https://pillars.taylor.edu/chemistry-student Part of the Analytical Chemistry Commons, Inorganic Chemistry Commons, Organic Chemistry Commons, Other Chemistry Commons, and the Physical Chemistry Commons CHEMISTRY THESIS SIGNIFICANCE AND IMPLICATIONS OF VITAMIN B-12 REACTION SCHEMA- ETH ZURICH VARIANT: MECHANISMS AND INSIGHTS DAVID JOSHUA FERGUSON 2019 2 Table of Contents: Chapter 1 6 Chapter 2 17 Chapter 3 40 Chapter 4 59 Chapter 5 82 Chapter 6 118 Chapter 7 122 Appendix References 3 Chapter 1 A. INTRODUCTION. Vitamin B-12 otherwise known as cyanocobalamin is a compound with synthetic elegance. Considering how it is composed of an aromatic macrocyclic corrin there are key features of this molecule that are observed either in its synthesis of in the biochemical reactions it plays a role in whether they be isomerization reactions or transfer reactions. In this paper the focus for the discussion will be on the history, chemical significance and total synthesis of vitamin B12. Even more so the paper will be concentrated one of the two variants of the vitamin B-12 synthesis, namely the ETH Zurich variant spearheaded by Albert Eschenmoser.Examining the structure as a whole it is observed that a large portion of the vitamin B12 is a corrin structure with a cobalt ion in the center of the macrocyclic part, and that same cobalt ion has cyanide ligands.
    [Show full text]
  • Rare-Earth Metal Methylidene Complexes with Ln3 (Μ3-CH2)(Μ3
    Dalton Transactions View Article Online PAPER View Journal | View Issue Rare-earth metal methylidene complexes with Ln3(μ3-CH2)(μ3-Me)(μ2-Me)3 core structure† Cite this: Dalton Trans., 2015, 44, 18101 Dorothea Schädle,a Melanie Meermann-Zimmermann,b Cäcilia Maichle-Mössmer,a Christoph Schädle,a Karl W. Törnroosc and Reiner Anwander*a Trinuclear rare-earth metal methylidene complexes with a Ln3(µ3-CH2)(µ3-Me)(µ2-Me)3 structural motif were synthesized by applying three protocols. Polymeric [LuMe3]n (1-Lu) reacts with the sterically demand- ing amine H[NSiMe3(Ar)] (Ar = C6H3iPr2-2,6) in tetrahydrofuran via methane elimination to afford isolable monomeric [NSiMe3(Ar)]LuMe2(thf)2 (4-Lu). The formation of trinuclear rare-earth metal tetramethyl methylidene complexes [NSiMe3(Ar)]3Ln3(µ3-CH2)(µ3-Me)(µ2-Me)3(thf)3 (7-Ln; Ln = Y, Ho, Lu) via reaction of [LnMe3]n (1-Ln; Ln = Y, Ho, Lu) with H[NSiMe3(Ar)] is proposed to occur via an “intermediate” species of the type [NSiMe3(Ar)]LnMe2(thf)x and subsequent C−H bond activation. Applying Lappert’s concept of Lewis base-induced methylaluminate cleavage, compounds [NSiMe3(Ar)]Ln(AlMe4)2 (5-Ln; Ln = Y, La, Nd, Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Ho) were converted into methylidene complexes 7-Ln (Ln = Y, Nd, Ho) in the presence of tetrahydrofuran. Similarly, tetramethylgallate complex [NSiMe3(Ar)]Y(GaMe4)2 (6-Y) could be employed as a synthesis pre- cursor for 7-Y. The molecular composition of complexes 4-Ln, 5-Ln, 6-Y and 7-Ln was confirmed by elemental analyses, FTIR spectroscopy, 1H and 13C NMR spectroscopy (except for holmium derivatives) Received 30th July 2015, and single-crystal X-ray diffraction.
    [Show full text]
  • Chapter 1 Tropone and Tropolone
    School of Molecular and Life Sciences New Routes to Troponoid Natural Products Jason Matthew Wells This thesis is presented for the Degree of Doctor of Philosophy of Curtin University November 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously pub- lished by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract Malaria is an infectious disease found in humans and other animals, it is caused by a single-cell parasite of the Plasmodium genus with many different substrains. Of these, P. falciparum is the most deadly to humans causing the majority of deaths. Although research into the area of antimalarial compounds is wide spread, few have been devel- oped with new structural features. Cordytropolone 37 is a natural product isolated in 2001 from the insect pathogenic fungus Cordyceps sp. BCC 1681 and has been shown to have antimalarial activity against P. falciparum. It has a structure unrelated to antimalarial com- pounds currently used in therapy. It does not contain a peroxide bridge as with artemisinin 25 or quinoline rings as with chloroquine 22. This unique structure indicates that it could possibly interact with the malaria parasite in a fashion unlike current treatments. In order for cordytropolone to be further developed as a potential treatment, it must first be synthe- sised in a laboratory environment. This study attempts to develop the first total synthesis of cordytropolone. H HO O N O O N O N H H H O O Cl HO O 22 25 37 Figure 0.0.1: Cordytropolone 37 has a unique structure compared to the current common malaria treatments The first method investigated towards the total synthesis of cordytropolone involved an intramolecular Buchner ring expansion.
    [Show full text]
  • Identification of a Novel Substrate-Derived Spermine
    ЭКСПЕРИМЕНТАЛЬНЫЕ СТАТЬИ UDK 577.152.1 Identification of a Novel Substrate- Derived Spermine Oxidase Inhibitor T. T. Dunston1, M. A. Khomutov2, S. B. Gabelli1,3,4, T. M. Stewart1, J. R. Foley1, S. N. Kochetkov2, A. R. Khomutov2*, R. A. Casero Jr.1* 1Sidney Kimmel Comprehensive Cancer Center, The Johns Hopkins University School of Medicine, Baltimore, MD 21287 USA 2Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, Moscow, 119991 Russia 3Department of Medicine, The Johns Hopkins University School of Medicine, Baltimore, MD 21205, USA 4Department of Oncology, The Johns Hopkins University School of Medicine, Baltimore, MD 21287, USA *E-mail: [email protected], [email protected] Received May 08, 2020; in final form, July 07, 2020 DOI: 10.32607/actanaturae.10992 ABSTRACT Homeostasis of the biogenic polyamines spermine (Spm) and spermidine (Spd), present in μM-mM concentrations in all eukaryotic cells, is precisely regulated by coordinated activities of the enzymes of poly- amine synthesis, degradation, and transport, in order to sustain normal cell growth and viability. Spermine oxidase (SMOX) is the key and most recently discovered enzyme of polyamine metabolism that plays an es- sential role in regulating polyamine homeostasis by catalyzing the back-conversion of Spm to Spd. The deve- lopment of many types of epithelial cancer is associated with inflammation, and disease-related inflammatory stimuli induce SMOX. MDL72527 is widely used in vitro and in vivo as an irreversible inhibitor of SMOX, but it is also potent towards N1-acetylpolyamine oxidase. Although SMOX has high substrate specificity, Spm analogues have not been systematically studied as enzyme inhibitors.
    [Show full text]
  • Trisubstituted Push-Pull Nitro Alkenes
    The Free Internet Journal Review for Organic Chemistry Archive for Arkivoc 2020, part vii, 401-421 Organic Chemistry Trisubstituted push-pull nitro alkenes Branislav Pavilek* and Viktor Milata Institute of Organic Chemistry, Catalysis, and Petrochemistry, Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, SK-812 37 Bratislava, Slovakia Email: [email protected] Dedicated to Professor Jan Bergman on the occasion of his 80th birthday. Received 02-18-2021 Accepted 04-19-2021 Published on line 04-30-2021 Abstract Properties, preparations, and utilization in the organic synthesis of the trisubstituted push-pull nitroalkenes are summarized from all the relevant results published until 2020. Preparation of these nitroalkenes is versatile due to numerous of the starting materials. The importance of reviewed nitroalkenes is outlined by their frequent exploitation in the synthesis of biologically active compounds, as well as a vast range of heterocyclic derivatives. Keywords: Push-pull nitroalkenes, nucleophilic vinylic substitution, heterocycles formation, nitroalkenes cycloadditions DOI: https://doi.org/10.24820/ark.5550190.p011.495 Page 401 ©AUTHOR(S) Arkivoc 2020, vii, 401-421 Pavilek, B. et al. Table of Contents 1. Introduction 2. Review 2.1. Isomerism 2.2. Preparation 2.2.1. Formation of nitroenolethers (A) 2.2.2. Formation of mono-N-substituted nitroenamines (B) 2.2.3. Formation of di-N,N-substituted nitroenamines (C) 2.2.4. Other preparations (D) 2.3. Utilization in organic synthesis 2.3.1. Reactions with mono-nucleophiles (E) 2.3.2. Reactions with 1,2-binucleophiles (F) 2.3.3. Reactions with 1,3-binucleophiles (G) 2.3.4.
    [Show full text]
  • Studies in Multicyclic Chemistry
    Studies in Multicyclic Chemistry This thesis is submitted in fulfillment of the requirements for the degree of Doctor of Philosophy by Djamal Sholeh Al Djaidi Supervisor Professor Roger Bishop School of Chemistry The University of New South Wales Sydney, Australia December, 2006 PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: AL DJAIDI First name: DJAMAL Other name/s: SHOLEH Abbreviation for degree as given in the University calendar: PhD School: CHEMISTRY Faculty: SCIENCE Title: STUDIES IN MULTICYCLIC CHEMISTRY Abstract 350 words maximum: (PLEASE TYPE) * A series of investigations has been carried out on multicyclic organic systems. The Ritter Reaction was used to obtain bridged imines containing an azacyclohexene functionality. The crystal structure of the benzene inclusion compound of one of these was determined, and also that of another spontaneously oxidised example. The reactivity of these bridged imines was then investigated using mercaptoacetic acid, and also dimethyl acetylenedicarboxylate (DMAD). The three bridged imines studied were found to react with DMAD in totally different ways and produced most unusual products whose structures were proved using X-ray crystallography. Mechanistic explanations are provided for the formation of these novel and totally unexpected products. * 6-Methylidene-3,3,7,7-tetramethylbicyclo[3.3.1]nonan-2-one was reacted with acetonitrile and sulfuric acid to deliberately combine molecular rearrangement with Ritter Reaction chemistry. Five different products were obtained and the pathway of formation of these products was uncovered. The structures of three of these rearranged substances were confirmed by X-ray methods. * The rare tricyclo[5.3.1.1 3,9]dodecane ring system is known to contain severe skeletal distortions due to the nature of its skeleton.
    [Show full text]
  • Electronic Or Optoelectronic Device Comprising an Anchored Thin Molecular Layer, Process for Its Preparation and Compound Used Therein
    (19) TZZ Z _T (11) EP 2 840 622 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) Int Cl.: 25.02.2015 Bulletin 2015/09 H01L 51/10 (2006.01) H01L 51/50 (2006.01) (21) Application number: 13180827.1 (22) Date of filing: 19.08.2013 (84) Designated Contracting States: • Lüssem, Björn AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 01127 Dresden (DE) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO •Leo,Karl PL PT RO RS SE SI SK SM TR 01219 Dresden (DE) Designated Extension States: • Fischer, Axel BA ME 01097 Dresden (DE) (71) Applicant: Novaled GmbH (74) Representative: Bittner, Thomas L. 01307 Dresden (DE) Boehmert & Boehmert Anwaltspartnerschaft mbB (72) Inventors: Patentanwälte Rechtsanwälte • Nicht, Sylvia Pettenkoferstrasse 20-22 01187 Dresden (DE) 80336 München (DE) •Blochwitz-Nimoth, Jan 01097 Dresden (DE) (54) Electronic or optoelectronic device comprising an anchored thin molecular layer, process for its preparation and compound used therein (57) The application concerns materials for self as- (EWG) group, such as tetrafluorotetracyanoquin- sembled (SAM) charge injection layers on electrodes of odimethane (F4TCNQ), hexaazatriphenylene (HAT) and organic electronic devices. The materials comprise an hexaazatriphenylene hexacarbonitrile (HATCN). The anchoring group, such as a thiol, a spacer group selected spacer group is connected to the EWG via a single bond from nitrogen aromatic heterocycles and aromatic rings from a nitrogen of the spacer group to a mehtylidenyl substituted with an amine, and an electron withdrawing group of the EWG. EP 2 840 622 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 840 622 A1 Description [0001] The present invention relates to an electronic or optoelectronic device comprising an anchored thin molecular layer.
    [Show full text]
  • Thiazolo[3,2-B][1,2,4]Triazolium Cationic Surfactant
    Article Volume 11, Issue 6, 2021, 13885 - 13892 https://doi.org/10.33263/BRIAC116.1388513892 Synthetic Strategy and Structure Characterization of a New [1,3]Thiazolo[3,2-b][1,2,4]Triazolium Cationic Surfactant Maksym Fizer 1,* , Mikhailo Slivka 2 , Oksana Fizer 3 1 Department of Organic Chemistry, Faculty of Chemistry, Uzhhorod National University, Fedinets', Str. 53/1, 88000, Uzhhorod, Ukraine; [email protected] (M.F.); [email protected] (M.S.); [email protected] (O.F.); * Correspondence: [email protected]; (M.F.); Scopus Author ID 55823743600 Received: 20.01.2021; Revised: 21.02.2021; Accepted: 24.02.2021; Published: 1.03.2021 Abstract: Here, we present a synthetic strategy to access a new [1,3]thiazolo[3,2-b][1,2,4]triazolium- based cationic surfactant via the use of proton-induced heterocyclization method for quaternization of a nitrogen atom. The two-step synthesis of 2-heptyl-6,6-dimethyl-3-phenyl-5,6-dihydro-3H- [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium perchlorate is described in details. The analysis of NMR spectra unequivocally proved the formation of the 1,3-thiazolinium ring upon cyclization reaction. PM7 semiempirical calculations testify to the similar electronic structure of the newly synthesized surfactant cation and 1-heptylpyridinium cation. Keywords: 1,2,4-triazole; alkylation; cyclization; surfactant; NMR; cation; PM7; semiempirical. © 2021 by the authors. This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
    [Show full text]
  • Towards the Synthesis of Isocoronene
    Department of Chemistry Towards the Synthesis of Isocoronene Iain William Currie This thesis is presented for the Degree of Doctor of Philosophy of Curtin University April 2018 Declaration To the best of my knowledge and belief this thesis contains no material previously published by any other person except where due acknowledgement has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any other university. Signature: Date: i Abstract The concept of aromaticity and its implications are fundamentally important to a wide range of applied sciences involving organic molecules. Aromaticity arises from the delocalisation of electrons through a cyclic conjugated system known as a conjugated circuit. Monocyclic aromatic compounds possess a single conjugated circuit while polycyclic aromatic hydrocarbons (PAHs) may have numerous potential conjugated circuits. The aromaticity of PAHs is complicated by the presence of multiple conjugated circuits which may have varying contribution to the overall properties depending on several factors such as geometry and topology. Isocoronene 105 is one example of a PAH classified as a non-benzenoid corannulene. Isocoronene is unique among corannulenes since the conjugated circuits are restricted to the peripheral and central rings only. Isocoronene has been used as a model compound for computational studies into aromaticity and may provide the first example of a superaromatic molecule. The synthesis of novel aromatic structures such as isocoronene is essential in providing unambiguous empirical data which can be used to verify and develop computational methods. In addition, the development of new synthetic methodologies towards PAHs is important in the field of organic electronics.
    [Show full text]
  • United States Patent (19) 11 Patent Number: 4,952,690 Gosteli Et Al
    United States Patent (19) 11 Patent Number: 4,952,690 Gosteli et al. 45) Date of Patent: Aug. 28, 1990 (54) 6-SUBSTITUTED THIA-AZA COMPOUNDS 4,447,360 5/1984 Gosteli et al. .................. 260/239 A 4,500,457 2/1985 Gosteli et al. ... 260/245.2 R 75 Inventors: Jacques Gosteli, Basel; Ivan Ernest, 4,515,717 5/1985 Gosteli et al. ..... as a s 260/239 A Birsfelden, both of Switzerland; 4,518,533 5/1985 Gosteli et al...... ... 260/245.4 Marc Lang, Mulhouse, France; 4,524,028 6/1985 Gosteli et al. ..... ... 260/239 A Robert B. Woodward, Cambridge, 4,543,257 9/1985 Cama et al. ... ... 540/310 ... 540/359 Mass. 4,614,614 9/1986 Ernest et al. 4,616,007 10/1986 Lang ................................... 514/192 73) Assignee: Ciba-Geigy Corporation, Ardsley, 4,656,165 4/1987 Lang ................................... 514/192 N.Y. 4,826,832 5/1989 Lang ................................... 540/310 21 Appl. No.: 396,783 Primary Examiner-Mark L. Berch (22 Filed: Aug. 21, 1989 Attorney, Agent, or Firm-JoAnn Villamizar 57) ABSTRACT Related U.S. Application Data The invention relates to azetidin-2-ones of the formula 60 Continuation of Ser. No. 152,526, Feb. 5, 1988, aban doned, which is a division of Ser. No. 57,082, Jun. 3, 1987, abandoned, which is a division of Ser. No. 208,105, Nov. 18, 1980, Pat. No. 4,692,442, which is a continuation of Ser. No. 7,453, Jan. 29, 1979, aban doned. (30) Foreign Application Priority Data Feb. 2, 1978 CH) Switzerland.....................
    [Show full text]
  • Understanding the Biosynthesis and Utilization of Non-Proteinogenic Amino Acids for the Production of Secondary Metabolites in Bacteria
    Understanding The Biosynthesis And Utilization Of Non-Proteinogenic Amino Acids For The Production Of Secondary Metabolites In Bacteria Author: Carl Victor Christianson Persistent link: http://hdl.handle.net/2345/967 This work is posted on eScholarship@BC, Boston College University Libraries. Boston College Electronic Thesis or Dissertation, 2008 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 UNDERSTANDING THE BIOSYNTHESIS AND UTILIZATION OF NON-PROTEINOGENIC AMINO ACIDS FOR THE PRODUCTION OF SECONDARY METABOLITES IN BACTERIA A dissertation by CARL VICTOR CHRISTIANSON Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy December 2008 © Copyright by CARL VICTOR CHRISTIANSON 2008 Acknowledgements I would like to than the members of my thesis defense committee, Jianmin Gao, Larry McLaughlin, and James Morken for taking time to critically read this thesis and to attend my defense. I am grateful to Professor Steven Bruner for accepting me into his lab and for his guidance over the past 5 years. Steve fostered an atmosphere of scientific discussion that challenged me to constantly learn new things. I admire Steve’s steady demeanor and am grateful to him for keeping me grounded and headed in the right direction. I would like to thank Timothy Montavon for carefully reviewing this thesis. Tim also contributed the synthetic projects that benefited the work presented in this thesis. Tim has always been there for helpful scientific discussions in the four years that we have been working together. I have been fortunate to work with a good group of students in the Bruner lab.
    [Show full text]
  • Decomposition of Ruthenium Olefin Metathesis Catalyst
    catalysts Review Decomposition of Ruthenium OlefinOlefin Metathesis CatalystMetathesis Catalyst Magdalena Jawiczuk 1,, Anna Anna Marczyk Marczyk 1,21,2 andand Bartosz Bartosz Trzaskowski Trzaskowski 1,* 1,* 1 1 CentreCentre of of New New Technologies, Technologies, University University of of Warsaw, Warsaw, Banacha Banacha 2c, 2c, 02-097 02-097 Warsaw, Warsaw, Poland; [email protected]@cent.uw.edu.pl (M.J.); (M.J.); [email protected] [email protected] (A.M.) (A.M.) 2 Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland 2 Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland * Correspondence: [email protected] * Correspondence: [email protected] Received: 28 28 June 2020; Accepted: 02 2 AugustAugust 2020;2020; Published:Published: 5date August 2020 Abstract: RutheniumRuthenium olefin olefin metathesis metathesis catalysts catalysts are are one one of of the most commonly used class of catalysts. There There are are multiple multiple reviews reviews on on their their us useses in in various branches of chemistry and other sciences but a detailed review of their decomposition is missing, despite a large number of recent and important advances advances in in this this field. field. In In particular, particular, in in the the last last five five years years several several new new mechanism mechanism of decomposition,of decomposition, both both olefin-driven olefin-driven as well as well as induc as induceded by external by external agents, agents, have have been been suggested suggested and usedand usedto explain to explain differences differences in the decomposition in the decomposition rates and rates the metathesis and the metathesis activities activitiesof both standard, of both N-heterocyclicstandard, N-heterocyclic carbene-based carbene-based systems and systems the recently and the developed recently developed cyclic alkyl cyclic amino alkyl carbene- amino containingcarbene-containing complexes.
    [Show full text]