Towards the Synthesis of Isocoronene
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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. -
Expanding the Scope of Thiophene Based Semiconductors: Perfluoroalkylated Materials and Fused Thienoacenes
Expanding the Scope of Thiophene Based Semiconductors: Perfluoroalkylated Materials and Fused Thienoacenes Hayden Thompson Black A dissertation submitted to the faculty of the University of North Carolina at Chapel Hill in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry Chapel Hill 2012 Approved By: Dr. Valerie Sheares Ashby Dr. James Cahoon Dr. Carrie Donley Dr. Wei You Dr. Malcolm Forbes ABSTRACT HAYDEN THOMPSON BLACK: Expanding the Scope of Thiophene Based Semiconductors: Perfluoroalkylated Materials and Fused thienoacenes (Under the direction of Valerie Sheares Ashby) Thiophene based semiconductors with new molecular and macromolecular structures were explored for applications in field effect transistors. Perfluoroalkylation was studied both as a means for controlling the self-assembly properties of polythiophenes, as well as modifying the molecular orbital energies of a series of oligothiophenes. End-perfluoroalkylation of poly(3-hexylthiophene) resulted in interesting self-assembly of the polymer into a bilayer vesicle. Similar fluorophilic assembly may be useful for controlling blend morphologies in heterojunction based devices. On the other hand, perfluoroalkylation of small molecule thiophene semiconductors leads to low lying LUMO levels, and can be used to promote electron injection for n-type transistor devices. This strategy was employed in combination with a π-electron deficient benzothiadiazole to afford a new n-type semiconductor with an exceptionally low LUMO. Monoperfluoroalkylated oligothiophenes were also synthesized and studied in field effect transistors for the first time. In addition, two new fused thienoacene compounds were synthesized and their crystal structures were analyzed. The fused compounds showed exceptional π-π stacking and assembled into well defined one-dimensional microcrystals from the vapor phase. -
Thiophene-Based Aldehyde Derivatives for Functionalizable
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Archive Ouverte en Sciences de l'Information et de la Communication Thiophene-based aldehyde derivatives for functionalizable & adhesive semiconducting polymers Emin Istif, Daniele Mantione, Lorenzo Vallan, Georges Hadziioannou, Cyril Brochon, Eric Cloutet, Eleni Pavlopoulou To cite this version: Emin Istif, Daniele Mantione, Lorenzo Vallan, Georges Hadziioannou, Cyril Brochon, et al.. Thiophene-based aldehyde derivatives for functionalizable & adhesive semiconducting polymers. ACS Applied Materials & Interfaces, Washington, D.C. : American Chemical Society, 2020, 10.1021/ac- sami.9b21058. hal-02467037 HAL Id: hal-02467037 https://hal.archives-ouvertes.fr/hal-02467037 Submitted on 4 Feb 2020 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. Thiophene-based aldehyde derivatives for functionalizable & adhesive semiconducting polymers Emin Istif,† Daniele Mantione,†* Lorenzo Vallan,† Georges Hadziioannou,† Cyril Brochon,† Eric Cloutet,†* and Eleni Pavlopoulou†* †Laboratoire de Chimie des Polymères Organiques (LCPO - UMR 5629), Bordeaux INP, Université de Bordeaux, CNRS, 16 Av. Pey-Berland, 33607, Pessac, France. Keywords EDOT-Aldehyde, thiophene-Aldehyde, PEDOT, conductive polymers, adhesion, electrode materials Abstract The pursuit for novelty in the field of (bio)electronics demands for new and better performing (semi)conductive materials. -
Insertion Reactions • Oxidative Addition and Substitution Allow Us to Assemble 1E and 2E Ligands on the Metal, Respectively
Insertion Reactions • Oxidative addition and substitution allow us to assemble 1e and 2e ligands on the metal, respectively. • With insertion, and its reverse reaction, elimination, we can now combine and transform these ligands within the coordination sphere, and ultimately expel these transformed ligands to form free organic compounds. • There are two main types of insertion 1) 1,1 insertion in which the metal and the X ligand end up bound to the same (,)(1,1) atom 2) 1,2 insertion in which the metal and the X ligand end up bound to adjacent (1,2) atoms of an L‐type ligand. 1 • The type of insertion observed in any given case depends on the nature of the 2e inserting ligand. • For example: CO gives only 1,1 insertion ethylene gives only 1,2 insertion, in which the M and the X end up on adjacent atoms of what was the 2e X‐type ligand. In general, η1 ligands tend to give 1,1 insertion and η2 ligands give 1,2 insertion • SO2 is the only common ligan d tha t can give bthboth types of itiinsertion; as a ligan d, SO2 can be η1 (S) or η2 (S, O). • In principle, insertion reactions are reversible, but just as we saw for oxidative addition and reductive elimination previously, for many ligands only one of the two possible directions is observed in practice, probably because this direction is strongly favored thermodynamically. 2 •A2e vacant site is generated by 1,1 and 1,2 insertion reactions. • Thissite can be occupidied byanextlternal 2e ligan d and the itiinsertion prodtduct tdtrapped. -
Insertion Reactions of Isocyanides Into the Metal-C(Sp3) Bonds of Ylide Complexes
Journal of Organometallic Chemistry 894 (2019) 61e66 Contents lists available at ScienceDirect Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem Insertion reactions of isocyanides into the Metal-C(sp3) bonds of ylide complexes ** * María-Teresa Chicote a, , Isabel Saura-Llamas a, , María-Francisca García-Yuste a, Delia Bautista b, Jose Vicente a a Grupo de Química Organometalica, Departamento de Química Inorganica, Facultad de Química, Universidad de Murcia, Spain b ACTI, Universidad de Murcia, E-30100, Murcia, Spain article info abstract Article history: The synthesis of the previously reported complexes [Pd{(C,CeCHCO2R)2PPh2}(m-Cl)]2 (R ¼ Me (1), Et (2)) Received 10 January 2019 has been considerably improved by reacting the phosphonium salts [Ph2P(CH2CO2R)2]Cl with Pd(OAc)2. Received in revised form t Complexes 1 and 2 react with isocyanides R'NC (R’ ¼ C6H4Me2-2,6 (Xy), C6H4I-2 and Bu) to give com- 29 April 2019 plexes of the type [Pd{C,C-{C(CO R) ¼ C(NHR0)}(CHCO R)}PPh }Cl(CNR0)], resulting from the insertion of Accepted 5 May 2019 2 2 2 the unsaturated molecule in one of their PdeC bonds and the hydrogen transfer from the methine CH to Available online 11 May 2019 the iminobenzoyl nitrogen. These are the first insertion reactions observed in the PdeC bond of a P-ylide complex. The crystal structure of the complex [Pd{C,C-{C(CO Me)¼C(NHXy)}(CHCO Me)}PPh }Cl(CNXy)] Keywords: 2 2 2 Palladacycles (3) is reported. © Insertion reactions 2019 Elsevier B.V. All rights reserved. -
Recent Advances on Mechanistic Studies on C–H Activation
Open Chem., 2018; 16: 1001–1058 Review Article Open Access Daniel Gallego*, Edwin A. Baquero Recent Advances on Mechanistic Studies on C–H Activation Catalyzed by Base Metals https:// doi.org/10.1515/chem-2018-0102 received March 26, 2018; accepted June 3, 2018. 1Introduction Abstract: During the last ten years, base metals have Application in organic synthesis of transition metal- become very attractive to the organometallic and catalytic catalyzed cross coupling reactions has been positioned community on activation of C-H bonds for their catalytic as one of the most important breakthroughs during the functionalization. In contrast to the statement that new millennia. The seminal works based on Pd–catalysts base metals differ on their mode of action most of the in the 70’s by Heck, Noyori and Suzuki set a new frontier manuscripts mistakenly rely on well-studied mechanisms between homogeneous catalysis and synthetic organic for precious metals while proposing plausible chemistry [1-5]. Late transition metals, mostly the precious mechanisms. Consequently, few literature examples metals, stand as the most versatile catalytic systems for a are found where a thorough mechanistic investigation variety of functionalization reactions demonstrating their have been conducted with strong support either by robustness in several applications in organic synthesis [6- theoretical calculations or experimentation. Therefore, 12]. Owing to the common interest in the catalysts mode we consider of highly scientific interest reviewing the of action by many research groups, nowadays we have a last advances on mechanistic studies on Fe, Co and Mn wide understanding of the mechanistic aspects of precious on C-H functionalization in order to get a deep insight on metal-catalyzed reactions. -
House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, Or Isothiocyanate Radicals
House Fly Attractants and Arrestante: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals Agriculture Handbook No. 403 Agricultural Research Service UNITED STATES DEPARTMENT OF AGRICULTURE Contents Page Methods 1 Results and discussion 3 Thiocyanic acid esters 8 Straight-chain nitriles 10 Propionitrile derivatives 10 Conclusions 24 Summary 25 Literature cited 26 This publication reports research involving pesticides. It does not contain recommendations for their use, nor does it imply that the uses discussed here have been registered. All uses of pesticides must be registered by appropriate State and Federal agencies before they can be recommended. CAUTION: Pesticides can be injurious to humans, domestic animals, desirable plants, and fish or other wildlife—if they are not handled or applied properly. Use all pesticides selectively and carefully. Follow recommended practices for the disposal of surplus pesticides and pesticide containers. ¿/áepé4áaUÁí^a¡eé —' ■ -"" TMK LABIL Mention of a proprietary product in this publication does not constitute a guarantee or warranty by the U.S. Department of Agriculture over other products not mentioned. Washington, D.C. Issued July 1971 For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 - Price 25 cents House Fly Attractants and Arrestants: Screening of Chemicals Possessing Cyanide, Thiocyanate, or Isothiocyanate Radicals BY M. S. MAYER, Entomology Research Division, Agricultural Research Service ^ Few chemicals possessing cyanide (-CN), thio- cyanate was slightly attractive to Musca domes- eyanate (-SCN), or isothiocyanate (~NCS) radi- tica, but it was considered to be one of the better cals have been tested as attractants for the house repellents for Phormia regina (Meigen). -
CH Functionalization Via Iron-Catalyzed Carbene
molecules Review C-H Functionalization via Iron-Catalyzed Carbene-Transfer Reactions Claire Empel, Sripati Jana and Rene M. Koenigs * Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany; [email protected] (C.E.); [email protected] (S.J.) * Correspondence: [email protected] Academic Editor: Hans-Joachim Knölker Received: 4 January 2020; Accepted: 5 February 2020; Published: 17 February 2020 Abstract: The direct C-H functionalization reaction is one of the most efficient strategies by which to introduce new functional groups into small organic molecules. Over time, iron complexes have emerged as versatile catalysts for carbine-transfer reactions with diazoalkanes under mild and sustainable reaction conditions. In this review, we discuss the advances that have been made using iron catalysts to perform C-H functionalization reactions with diazoalkanes. We give an overview of early examples employing stoichiometric iron carbene complexes and continue with recent advances in the C-H functionalization of C(sp2)-H and C(sp3)-H bonds, concluding with the latest developments in enzymatic C-H functionalization reactions using iron-heme-containing enzymes. Keywords: iron; carbene; diazoalkane; C-H functionalization 1. Introduction C-H bonds belong to the most common motifs in organic molecules and their direct functionalization is one of the main challenges in synthesis methodology, which impacts on the step economy and sustainability of chemical processes. In recent decades, this research area has flourished and different approaches have been realized to enable C-H functionalization reactions via different strategies: (a) by the directing group-assisted C-H activation, (b) via the innate reactivity of organic molecules, or (c) via direct C-H functionalization (Scheme1)[ 1–4]. -
A DFT Study on Sumanene, Corannulene and Nanosheet As the Anodes in Li−Ion Batteries
Iran. J. Chem. Chem. Eng. Research Article Vol. 39, No. 6, 2020 Archive of SID A DFT study on Sumanene, Corannulene and Nanosheet as the Anodes in Li−Ion Batteries Gharibzadeh, Fatemeh Department of Chemistry, Tabriz Branch, Islamic Azad University, Tabriz, I.R. IRAN Vessally, Esmail Department of Chemistry, Payame Noor University, Tehran, I.R. IRAN Edjlali, Ladan*+; Es’haghi, Moosa Department of Chemistry, Tabriz Branch, Islamic Azad University, Tabriz, I.R. IRAN Mohammadi, Robab Department of Chemistry, Payame Noor University, Tehran, I.R. IRAN ABSTRACT: Herein, we studied interactions between the Li neutral atom and Li+ ion and three types of nanoparticles including sumanene (Sum), corannulene (Cor), and nanosheet to obtain the cell voltage (V) for Li−ion batteries (LIBs). Total energies, geometry optimizations, Frontier Molecular Orbital (FMO), and Density of States (DOS) analyses have been obtained using M06−2X level of theory and 6−31+G (d,p) basis set. DFT calculations clarified that the changes of energy + adsorption between Li ion and nanoparticles, Ead, are in the order: Sheet > Sum−I > Cor > Cor−I > Sum. However, the Vcell for Sum is the highest. The changes in Vcell of Li−ion batteries (LIBs) are in the order: Sum > Sheet > Sum−i > Cor > Cor−i. This study theoretically indicates the possibility of Li as the anode in the battery field. KEYWORDS: DFT study; Sumanene; Corannulene; Nanosheet; Li−ion Batteries. INTRODUCTION Rechargeable batteries are very important to batteries due to its low density, high specific capacity, generation the electricity. The dry batteries, such as Zn−C, and the lowest electrochemical potential of the periodic table [1]. -
Abstract(Doctor)
別紙4-1(課程博士(英文)) Date of Submission(month day,year): March 27, 2020 Department Applied Chemistry and Life Student ID Number D 169403 SEIJI IWASA Science Supervisors KAZUTAKA SHIBATOMI Applicant’s name PHAN THI THANH NGA Abstract(Doctor) Catalytic Intramolecular Carbene Transfer Reactions into σ and π Bonds Title of Thesis (σ 及びπ結合への触媒的分子内カルベン移動反応) Approx. 800 words A carbene known as an most active intermediate is complexed with a transition metal, which afford the corresponding metal-carbene complex and catalytically insert into σ and π bonds of organic compound. Even though there are many reports on the carbene transfer process to develop a new approach for the synthesis of medicine and other bioactive compounds, the regio-, stereo- and chemoselective approaches are still limited and remained as a main subject in the filed of synthetic organic chemistry. For these background, I developed an efficient catalytic intramolecular carbene transfer reactions by using originally developed ruthenium catalyst into σ and π bonds and successfully applied for the synthesis of γ-lactam ring fused aromatics (oxindoles), γ-lactone ring fused cyclopropanes, and γ-lactam ring fused seven member rings via Buchner reaction. Although ruthenium complex is a newcomer in the field of catalytic carbene transfer reaction, it has emerged as a useful transition metal for the carbenoid chemistry of diazo compounds, besides copper and rhodium. And recently, we have developed a Ru(II)-Pheox complex, which is efficient for carbene transfer reactions, in particular, asymmetric cyclopropanation, N-H insertion, C-H insertion and Si-H insertion reactions. Therefore, driven by my interests in the catalytic asymmetric carbene transfer reaction and the efficiency displayed by the Ru(II)-Pheox catalyst, I started to explore the asymmetric cyclopropanation, C-H insertion, Buchner reactions of various diazo compounds, which are potentially building blocks and expectant to be applied in pharmaceutical and medicinal fields . -
Enantioselective Synthesis of a Chiral Nitrogen-Doped Buckybowl
ARTICLE Received 9 Mar 2012 | Accepted 9 May 2012 | Published 12 Jun 2012 DOI: 10.1038/ncomms1896 Enantioselective synthesis of a chiral nitrogen- doped buckybowl Qitao Tan1, Shuhei Higashibayashi1,2, Sangita Karanjit2 & Hidehiro Sakurai1,2 Bowl-shaped aromatic compounds, namely buckybowls constitute a family of curved polycyclic aromatic carbons along with fullerenes and carbon nanotubes. Doping of heteroatoms to the carbon frameworks of such aromatic compounds drastically modulates their physical and chemical properties. In contrast to nitrogen-doped azafullerenes or carbon nanotubes, synthesis of azabuckybowls, nitrogen-doped buckybowls, remains an unsolved challenging task. Here we report the first enantioselective synthesis of a chiral azabuckybowl, triazasumanene. X-ray crystallographic analysis confirmed that the doping of nitrogen induces a more curved and deeper bowl structure than in all-carbon buckybowls. As a result of the deeper bowl structure, the activation energy for the bowl inversion (thermal flipping of the bowl structure) reaches an extraordinarily high value (42.2 kcal per mol). As the bowl inversion corresponds to the racemization process for chiral buckybowls, this high bowl inversion energy leads to very stable chirality of triazasumanene. 1 Research Center for Molecular Scale Nanoscience, Institute for Molecular Science, Myodaiji, Okazaki 444-8787, Japan. 2 School of Physical Sciences, the Graduate University for Advanced Studies, Myodaiji, Okazaki 444-8787, Japan. Correspondence and requests for materials should be addressed to S.H. (email: [email protected]). NATURE COMMUNICATIONS | 3:891 | DOI: 10.1038/ncomms1896 | www.nature.com/naturecommunications © 2012 Macmillan Publishers Limited. All rights reserved. ARTICLE NatUre cOMMUNicatiONS | DOI: 10.1038/ncomms1896 olycyclic aromatic carbons with curved π-conjugated struc- R N tures, such as fullerenes and carbon nanotubes (CNTs), exhibit Pfascinating physicochemical properties especially in material science1–3. -
Carbene Rearrangements: Intramolecular Interaction of a Triple Bond with a Carbene Center
An Abstract OF THE THESIS OF Jose C. Danino for the degree of Doctor of Philosophy in Chemistry presented on _Dcc, Title: Carbene RearrangementE) Intramolecular Interaction of a Triple Bond with aCarbene Center Redacted for Privacy Abstract approved: Dr. Vetere. Freeman The tosylhydrazones of2-heptanone, 4,4-dimethy1-2- heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2- one were synthesizedand decomposed under a varietyof reaction conditions:' drylithium and sodium salt pyrolyses, sodium methoxide thermolysesin diglyme and photolyses of the lithium salt intetrahydrofuran. The saturated ana- logues 2-heptanone tosylhydrazoneand its 4,4-dimethyl isomer afforded the alkenesarising from 6-hydrogeninser- product distribution in the tion. It was determined that differ- dry salt pyrolyses of2-heptanone tosylhydrazone was ent for the lithiumand the sodium salts. However, the product distribution of thedry sodium salt was verysimilar diglyme to product distributionobtained on thermolysis in explained by a with sodium methoxide. This difference was reaction of lithium bromide(present as an impurity inall compound to the lithium salts)with the intermediate diazo afford an organolithiumintermediate that behaves in a some- what different fashionthan the free carbene.The unsaturated analogues were found to produce a cyclic product in addition to the expected acyclic alkenes arising from 3-hydrogen insertion. By comparison of the acyclic alkene distri- bution obtained in the saturated analogues with those in the unsaturated analogues, it was concluded that at leastsome cyclization was occurring via addition of the diazo moiety to the triple bond. It was determined that the organo- lithium intermediateresulting from lithium bromide cat- alyzed decomposition of the diazo compound was incapable of cyclization.