Synthesis, Characterization, and Reactivity of Cross-Conjugated Frameworks
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
Deoxygenation Supplemental Without Spectra
Novel Organic Transformations Arising from Gold(I) Chemistry By Mathieu André Morin Thesis submitted to the faculty of Graduate and Postdoctoral Studies In partial fulfillment of the requirements for the Ph.D. degree in chemistry Candidate Supervisor Mathieu André Morin Dr. Louis Barriault Ottawa-Carleton Chemistry Institute Faculty of Science University of Ottawa © Mathieu André Morin, Ottawa, Canada, 2017 Abstract The use of gold in organic chemistry is a relatively recent occurrence. In addition to being previously considered too expensive, it was also believed to be chemically inert. Soon after the early reports indicating its rich reactivity, the number of reports on chemical transformations involving gold sky rocketed. One such report by Toste and coworkers demonstrated the intramolecular addition of silyl enol ether onto Au(I) activated alkynes, resulting in a 5-exo dig cyclization. The first part (Chapter 1) of this thesis discusses the development of a Au(I) catalyzed polycyclization reaction inspired by this transformation. The reaction demonstrated the ability of Au(I) to successfully catalyze the formation of multiple C-C bonds and resulted in the synthesis of benzothiophenes, benzofurans, carbazoles and hydrindene. With the current resurgence of photochemical transformations being reported in literature, various opportunities for the use of Au(I) complexes arose. The substantial relativistic effect observed in gold which make it a good soft Lewis acid also has a significant influence on the redox potential of this metal. Chapter 3 of this thesis discusses the development of a Au(I) photocatalyzed process which benefits from having both a strong oxidation and reduction potential for the reduction of carbon-halide bonds. -
A General Synthesis of Dendralenes†
Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue A general synthesis of dendralenes† Cite this: Chem. Sci.,2019,10, 9969 Josemon George, Jas S. Ward and Michael S. Sherburn * All publication charges for this article The first general synthetic approach to substituted [3]- and higher dendralenes is reported. Fifty-one mono- have been paid for by the Royal Society of Chemistry through to penta-substituted dendralenes carrying alkyl-, cycloalkyl-, alkenyl-, alkynyl-, aryl- and heteroaryl-substitutents are accessed, and the first (E)/(Z)-stereoselective syntheses of dendralenes are reported (twenty-eight examples). The approach involves twofold Pd(0)-catalyzed Negishi couplings of Received 9th August 2019 1,1-dibromoalkenes with alkenylzinc reagents, and exploits both substrate- and catalyst-controlled Accepted 11th September 2019 aspects of chemo-, regio- and stereoselectivity in the two C(sp2)–C(sp2) bond forming steps. The value DOI: 10.1039/c9sc03976g of the new hydrocarbons in rapid structural complexity generation is demonstrated through their rsc.li/chemical-science deployment in unprecedented diene- and triene-transmissive pericyclic reaction sequences. Introduction undergo sequential additions in an interconnected (i.e. diene- transmissive) manner.3,8,9 Creative Commons Attribution 3.0 Unported Licence. In hydrocarbons comprising carbon atoms that are sp2 As the potential of dendralenes has been more widely hybridized, the absence or presence of chain bifurcations and recognized, numerous publications focusing on dendralene 10 rings permit four fundamental structural families to be synthesis have recently appeared. The rapid expansion of designed (Fig. 1).1 Dendralenes are the acyclic, branched class interest in dendralenes, combined with the paucity of synthetic of structures that, until the turn of this century, were widely methods to access them, renders the recent contributions perceived to be unmanageable.2,3 [3]Dendralene through [12] signicant. -
Fullerene-Acene Chemistry
University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2007 Fullerene-acene chemistry: Part I Studies on the regioselective reduction of acenes and acene quinones; Part II Progress toward the synthesis of large acenes and their Diels-Alder chemistry with [60]fullerene Andreas John Athans University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Athans, Andreas John, "Fullerene-acene chemistry: Part I Studies on the regioselective reduction of acenes and acene quinones; Part II Progress toward the synthesis of large acenes and their Diels-Alder chemistry with [60]fullerene" (2007). Doctoral Dissertations. 363. https://scholars.unh.edu/dissertation/363 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. FULLERENE-ACENE CHEMISTRY: PART I: STUDIES ON THE REGIOSELECTIVE REDUCTION OF ACENES AND ACENE QUINONES; PART II: PROGRESS TOWARD THE SYNTHESIS OF LARGE ACENES AND THEIR DIELS- ALDER CHEMISTRY WITH [60]FULLERENE VOLUME 1 CHAPTERS 1-5 BY ANDREAS JOHN ATHANS B.S. University of New Hampshire, 2001 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy m Chemistry May, 2007 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3 2 6 0 5 8 6 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. -
A Study of [3] Dendralene, Its Synthesis and Applications
A STUDY OF [3] DENDRALENE, ITS SYNTHESIS AND APPLICATIONS by Susannah M. Gillam Thesis presented for the degree of Doctor of Philosophy University of Edinburgh January 1990 fk 9 To my parents and my sister for their continuous support DECLARATION I declare that this thesis is my own composition, that it is a record of the work which has been carried out by myself, and that it has not been submitted in any previous application for a higher degree. The thesis describes the results of research carried out in the Department of Chemistry, University of Edinburgh, under the supervision of Dr. I. Gosney since 1st October 1986, the date of my admission as a research student. POST-GRADUATE LECTURE COURSES The following is a statement of the courses attended during the period of research: - Organic Research seminars (3 years attendance) - Current Topics in Organic Chemistry, various lecturers, (15 lectures) - Strategy of Synthesis, Dr. I. Gosney (5 lectures). - Structural Elucidation, Dr. D. Leaver (5 lectures) - Mass Spectrornetry, Prof. K.R. Jennings (5 lectures). - Medicinal Chemistry, Prof. P.G. Sammes, 1988 (5 lectures). - Medicinal Chemistry, Dr. P. Leeson and Dr. R. Baker, 1989, (5 lectures). - Recent Advances in Organic Chemistry, various speakers (5 lectures). - Multipulse n.m.r. Spectroscopy, Dr. I. Sadler (5 lectures). - Two Dimensional n.m.r. Spectroscopy, Dr. I. Sadler, Dr. R. Baxter and Dr. B. Birdsall (5 lectures). Attended and passed the Scientific German Course 1987. ACKNOWLEDGEMENTS I would like to thank my Ph.D. supervisor Dr. Ian Gosney for his help and support throughout this work. I would also like to extend my thanks to the technical staff here at the University of Edinburgh and particularly to J. -
An Overview of Fullerene Chemistry
Bull. Mater. So., Vol. 20, No. 2, April 1997, pp. 141-230. © Printed in India. An overview of fullerene chemistry S SAMAL* and S K SAHOO Department of Chemistry, gavenshawCollege, Cuttack 753 003, India MS received 4 April 1996; revised 3 October 1996 Abstract. Fullerenes which were thought to be 'superaromatics' are actually 'super- alkenes'. Reactions in fuUerenesare varied, ranging from the addition of simple molecules like H 2 to large moleculeslike dendrimers.The synthesis,structure, characterization,along with simple reactions like halogenation, oxygenation, metalation,cydoaddition, polymeri- zation and dendrimer addition are discussed. Keywards. Fullerenes;C6o; C7o; characterization;reactions. 1. Introduction Fullerenes and their derivatives possess a number of potentially useful physical, biological and chemical properties. Our interest in the chemistry of fullerenes led us to present this review in which we have attempted to furnish an overall picture of the properties of these novel molecules. The scope of the review is however limited. The conclusion of the authors contributing to this rapidly growing field of research are accepted and presented in a concise manner highlighting the salient features of the original work. The technique developed by Kr/itschmer et al (1990) for preparing and isolating macroscopic quantities of C6o, 'a new form of carbon', opened the way for exploring the molecular and bulk properties of these novel species. Kroto et al (1985) reported the nature and chemical reactivity of C6o species produced during the nucleation of carbon plasma. C6o , which was found to be stable, was named buckminsterfullerene after Buckminster Fuller, American architect, engineer and constructor of geodesic dome. -
Sulfolane: Magic Extractor Or Bad Actor? Pilot-Scale Study on Solvent Corrosion Potential
sustainability Review Sulfolane: Magic Extractor or Bad Actor? Pilot-Scale Study on Solvent Corrosion Potential Andrzej Bak 1,* , Violetta Kozik 1, Paulina Dybal 1, Slawomir Kus 2, Aleksandra Swietlicka 1 and Josef Jampilek 3,* 1 Department of Synthesis Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Szkolna 9, 40007 Katowice, Poland; [email protected] (V.K.); [email protected] (P.D.); [email protected] (A.S.) 2 Honeywell Process Solutions, 11201 Greens Crossing Blvd, Suite 700 Houston, TX 77067, USA; [email protected] 3 Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Comenius University, Odbojarov 10, 83232 Bratislava, Slovakia * Correspondence: [email protected] (A.B.); [email protected] (J.J.); Tel.: +48-32-359-1197 (A.B.) Received: 17 September 2018; Accepted: 11 October 2018; Published: 14 October 2018 Abstract: The sulfur-containing derivatives and their metabolites, regarded as ‘old devils of green’ chemistry, constitute a relevant class of air/water/soil contaminants in over-polluted world. In fact, some industrially-engineered solvents have become environmentally unfavorable. An attractive alternative to commonly used industrial liquids is sulfolane (C4H8SO2), an anthropogenic medium. The main objective of this paper is the comprehensive review focusing mainly on the state-of-the-art aspects of the sulfolane synthesis, application of sulfolane as an extractive solvent due to its ‘unique’ physicochemical properties as well as the potential of sulfolane to cause equipment corrosion and subsequent spills. The potential risk for groundwater contamination, danger for human health and ways of sulfolane biodegradation were briefly reviewed as well. Interestingly, the analysis performed on data stored in the Reaxys database revealed an alternating tendency of waxing and waning interest in sulfolane during the space of the last fifty years. -
Fluorinated Butatrienes
Fluorinated Butatrienes Dissertation zur Erlangung des akademischen Grades des Doktors der Naturwissenschaften (Dr. rer. nat.) eingereicht im Fachbereich Biologie, Chemie, Pharmazie der Freien Universität Berlin vorgelegt von Dipl.-Chem. Christian Ehm aus Berlin Berlin, April 2010 1. Gutachter: Prof. Dr. Dieter Lentz 2. Gutachter: Prof. Dr. Beate Paulus Disputation am 28.6.2010 I Acknowledgements It would not have been possible to write this doctoral thesis without the help and support of the kind people around me, to only some of whom it is possible to give particular mention here. First and foremost I would like to thank my principal supervisor, Professor Dieter Lentz, for the opportunity of doing research in his group. Without his continuous support and encouragement this thesis would not be in the present state. I highly appreciate that Professor Beate Paulus has agreed to be co-referee of my thesis. I would like to cordially thank Lada for her love and patience as well as her interest in my research. Special thanks to my family for their continuous support and love. I would like to thank Mike Roland, Sten Dathe and Sven Wünsche for their friendship and the fun we have had every Sunday evening. Special thanks to Sebastian Freitag, Boris Bolsinger and Frederic Heinrich for their friendship. They deserve much gratefulness for keeping me on the right way. I would like to thank all my colleagues at the Institut für Chemie und Biochemie, Abteilung Anorganische Chemie. In particular I want to thank all members of the Lentz group, Thomas Hügle, Moritz Kühnel, Dr. Floris Akkerman, Dr. -
Rudo-At-Thur a 77OAPAVA 1S Patented Dec
Dec. 11, 1951 J. E. MAHAN ET AL 2,578,565 HYDROGENATING SULFOLENES TO SULFOLANES Filed Dec. 28, 1948 o g X g t 92.9 DVOS a dig NGOOOH Ofse INVENTORS J.E. MAHAN BY S.C. FAUSKE Rudo-at-thur A 77OAPAVA 1S Patented Dec. 11, 1951 2,578,565 UNITED STATES PATENT OFFICE 2,578,565 HYDROGENATING SULFOLENESTO SULFOLANES John E. Mahan and Sig C. Fauske, Bartlesville, Okla., assignors to Phillips Petroleum Company, a corporation of Delaware Application December 28, 1948, Serial No. 67,745 15 Claims. (CI. 260-332.1) 1. 2 This invention relates to the production of the generic term “a sulfolane' or "a Sulfolane Sulfolanes by the hydrogenation of the corre compound' covering not only the above Com sponding unsaturated Sulfolenes. In One par pound but also the substituted derivatives there ticular embodiment it relates to an improved of, particularly those in which various radicals process for the production of 2,3,4,5-tetrahy mentioned in the preceding paragraph are Sub drothiophene-1,1-dioxide, commercially known stituted for one or more of the hydrogen atoms as sulfolane, by the catalytic hydrogenation of of the above structure. Where such a radical the corresponding unsaturated cyclic butadiene is hydrogenatable under the conditions of our monosulfone, i. e. 2,5-dihydrothiophene-1,1- process, it will be understood that the sulfolane dioxide, commercially known as Sulfolene, in the 0. containing the hydrogenated radical is included presence of a novel solvent. when reference is made to a sulfolane compound The term “a sulfolene compound' as employed which “corresponds' to a given sulfolene com herein and in the appended claims, defines ge pound. -
Core and Double Bond Functionalisation of Cyclopentadithiophene-Phosphaalkenes†‡ Cite This: Inorg
Volume 7 | Number 21 | 7 November 2020 INORGANIC CHEMISTRY FRONTIERS rsc.li/frontiers-inorganic INORGANIC CHEMISTRY FRONTIERS View Article Online RESEARCH ARTICLE View Journal | View Issue Core and double bond functionalisation of cyclopentadithiophene-phosphaalkenes†‡ Cite this: Inorg. Chem. Front., 2020, 7, 4052 Jordann A. L. Wells, § Muhammad Anwar Shameem, ¶§ Arvind Kumar Gupta and Andreas Orthaber * The heterofulvenoid cyclopentadithiophene-phosphaalkene is a versatile building block for opto-elec- tronic tuning with donor and acceptor moieties. Both the annulated thienyl rings and the phosphaalkene Received 17th June 2020, bond can be functionalised using a variety of chemical transformations, e.g. forming C–C, C–E(EvSi, Br) Accepted 7th September 2020 bonds, or oxidation and metal coordination, respectively. Solid-state structures, optical and electronic DOI: 10.1039/d0qi00714e properties are probed theoretically and experimentally, illustrating the opto-electronic tailoring opportu- rsc.li/frontiers-inorganic nities at this motif. 7–9 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Introduction phosphaalkenes. The introduction of this group 15 heteroe- lement as part of conjugated frameworks has noticeable stabi- Combining electron donor and electron acceptor units to tailor lising effects on the LUMO levels, while the HOMO remains the HOMO and LUMO of dye molecules has been an exten- almost unaltered. In these building blocks, the low-lying het- sively used concept in the design of dyes for sensors, solar eroalkene π* orbitals provide an acceptor group resulting in cells, etc.1 In the cyclopentadithiophene (CPDT) motif two properties applicable to opto-electronic materials.10,11 The thiophene units are linked using a methylene bridge improv- marked difference to its lighter homologue, i.e. -
Organic Cumulative Exam October 15, 2015
Organic Cumulative Exam October 15, 2015 Answer only three of the six questions. No more than three question answers will be graded and any work not to be considered must be marked as such. Clearly indicate which questions are to be graded on the front of your answer booklet. 1. (33 points) Sherburn, Paddon–Row, and co-workers recently disclosed a synthesis of pseudopterosin aglycones. The synthetic route is shown schematically below. Nature Chem. 2015, 7, 82–86. A. Give the structure of intermediates A – H (be sure to indicate stereochem). B. Show how the starting material (SM) could be prepared as a single enantiomer. C. Two steps used high pressure (19 kbar). Explain why high pressure was successful in promoting these particular transformations (be specific). D. Show the curved arrow mechanism for the transformation F ! G.# Ni(dppp)Cl2 Ph3P, THF MeOH –20 oC 19 kbar, CH2Cl2 A B CO Et O Me OHC 2 CHO S BrMg (C10H14) SM O O RhCl(Ph3P)3 (2.5 mol%) nPrCN, 119 oC DIBAL (1 equiv.); 19 kbar, CH2Cl2 C D E F then: NO2 Ph3P (C17H26O2) tBuOK, THF, KHMDS, THF (COCl)2, DMSO o H then H O, –78 oC, then: Et3N, CH2Cl2, –78 C OH 2 G H then: O O O TsN (C H O ) OH Ph 20 30 2 pseudopterosin G aglycone 2. (33 points) (a) Please provide a complete mechanism for the following transformation recently reported by Seidel and co-workers. J. Org. Chem. 2015, 80, 9628-9640. O Ph AcOH PhMe N 52% NO2 NH H 9:1 dr 4 Å MS O2N 1 2 reflux, 1 h 3 Ph (b) Seidel reported the application of this method for a short synthesis of (–)-protoemetinol. -