Diazo-Mediated Metal Carbenoid Chemistry ~Recent Developments of Variety Bond Formation Methods~

Total Page:16

File Type:pdf, Size:1020Kb

Diazo-Mediated Metal Carbenoid Chemistry ~Recent Developments of Variety Bond Formation Methods~ Literature Seminar (D2 Part) 2011/04/06 (Wed) Noriaki Takasu (D2) Diazo-mediated Metal Carbenoid Chemistry ~Recent Developments of Variety Bond Formation Methods~ Cyclopropanation C-H Insertion [4+3] Cyclization R1 R2 N2 R1 LnM 2 LnM R [3+2] Cyclization Metal Carbenoid Ylide Formation Coupling N-H, O-H Insertion Recently, many metal catalyzed C-H activation reactions have been reported, but many reactions have not become reaction using wide range (selectivity, functional group tolerance). The metal-carbenoid intermediates are capable of undergoing a range of unconventional reactions, and due to their high energy, they are ideal for initiating cascade sequences leading to the rapid generation of structural complexity. These species are using for many type C-H activated reactions, C-C or C-heteroatom bond formations, and skeletal constructions. In this seminar, I talk about many type metal-carbenoid reactions from various metal. Contents 1. Carbenoid (P.1-2) 2. Rhodium Carbenoid Induced Reaction (P.3-10) 3. Copper Carbenoid Induced Reaction (P.11-12) 4. Palladium Carbenoid Induced Reaction (P.13-14) 5. Other Metal Carbenoid Induced Reaction (P.15-16) 6. Summary & Perspective (P.17) 1. Carbenoid 1-1. Carbene Carbene is a molecule containing a neutral carbon with a 2 valences R NN R R and 2 unshared electrons. C Carbenes are classified as either singlets or triprets depending upon their NHC R' electronic structure. Most carbenes are very short lived, although persistent carbenes are ref.) Nojiri's Lit known (example of stable carbene: N-Heterocyclic carbene; NHC). (M1 Part) p p R R Singlet Triplet R' R' • unshared electron pair ( orbital) and empty p orbital • 2 electron was shared with p orbital and orbital • resembles carbocation and carboanion united on same • resembles biradical carbon, so have nucleophilicity and electrophilicity • Typical angle (calculated) : 130~150° (reactivity depends on substituted groups). • many R and R' groups can stabilize singlet carbene (more than triplet carbene). • Typical angle (calculated) : 100~110° One of the typical carbene formation : diazo decomposition Diazo compounds readily decompose thermally or photochemically N or h or Metal CO2R N CO2R driving force : formation of N2 bond and generation of N2 gas -N H Generated carbene is high reactivity. H 2 In the case of using transition metal to generated carbene C-H Insertion Metal-Carbenoid species is generated 1,2-migration of alkyl Cyclopropanylation and other reaction... 1-2. Metal-Carbenoid Carbenoid is a vague term used for a molecule in which all carbons are tetravalent but still has properties resembling those of a carbene, typically the carbene-like carbon has multiple bonds with a metal. Carbene is stabilized by Metal. Carbenoid has unique reactivity that carbene has not, keeping the reactivity of free carbene. Carbenoid is structurally related to singlet carbenes and posses similarly reactivity. R Carbenoids can be formed by reacting salts of transition metals. e.g. Cu, Rh, Pd, etc... many metals can be formed. MLn These are formed by metal with carbenoid precursor, typically diazo compound. R' Kind of Diazo Compound (Carbenoid Precursor) Carbenoid can be controled carbene reactivity through substituent (acceptors and donors). Not enough electrophilicity causes less reactivity, and too much electrophilicity causes side-reaction, so control of electrophilicity is important. Metal-carbenoid reaction requires appropriate level of electrophilic ability at the carbenoid carbon center. Acceptor Acceptor/Acceptor Acceptor/Donor •Acceptor/Acceptor and Acceptor/Donor types stabilize O O O O diazo compound (so more active catalyst needed for decomposition). H Y X X Y X • Donor substituent stabilized carbenoid through resonance. N2 N2 N2 • Almost metal-carbenoids have electrophilicity. X = R, OR, NR2 X, Y = R, OR, NR2 X = R, OR, NR2 • Carbenoids formed from Acceptor/Acceptor compounds Y = vinyl, Aryl has high electrophilicity. too much electrophilicity causes side-reaction, so control of electrophilicity is important. Electron Feature of This Type Metal-Carbenoid R lone pair on carbon to M : strong C-M bond M C d electrons to p orbital on carbon : weak~moderate bond, stabilize carbene a little R' but still maintain its enough electrophilicity desired metal : bind to the carbene through strong -acceptor interactions and weak (appropriate) back donation interaction. 1/17 Observation of Carbenoid Cu-Carbenoid P. Hofmann et al., ACIE, 2001, 40, 1288. TMS TMS CO Me CO Me tBu N 2 tBu N 2 2 P Cu + N P Cu tBu 2 tBu N Ph N Ph 5 TMS TMS Cu-Carbenoid In toliene-d8 or benzene-d6 at rt, 15-25% Cu-complex was detected. atropisomer Caractarization from 1H NMR (Figure 2), 13C NMR (229.9 ppm of 5 + (C=N2), 177.9 ppm (C=O), MS (FAB; 531.2, [M ]). (At -33 C, this comoplex was maintained for several hours without significant evolution of nitrogen.) Rh2-Carbenoid J. P. Snyder et al., JACS, 2001, 123, 11318. tBu O tBu N O O Rh (OCOtBu) + Rh O 2 4 toluene O Rh Me X-ray structure N O N rt t O MeN Bu O tBu 1-3. Early Example of Metal-Carbenoid Reaction Insertion P. Yate, JACS, 1952, 74, 5376. :NuH O Cu O O -N2 N2 H H R R Nu = RO, RS, R2N R (complex with Cu) Nu Cyclopropanyration Cl A. F. Noels et al., Tetrahedron, 1983, 39, 2169. Cl Metal Metal; Cl Rh (OAc) : 54% 2 4 In this paper, other example, Cl N HC CO R Cu(OTf) : 42% 2 2 2 reactivity is [Rh] > [Cu] > [Pd] Pd(OAc)2 : 12% CO2R Dimerization (Homometathesis) Ph Ph Ph O O Cu + N OO 2 toluene Ph Ph Ph 86% R. Noyori et al., TL, 1966, 1, 59. general metal of metal-carbenoid reaction : Rh, Cu, Pd ; most useful metal is Rhodium. Dirhodium carboxylate (Rh2L4) H. Reimlinger et al., TL, 1973, 24, 2233. Catalyst diazo/Catalyst R Yield First example of Rhodium carbenoid generation from diazo decomposition. Rh2(OAc)4 600 Et 88 catalyst i R OH + N CO Et RO CO Et Rh2(OAc)4 600 Pr 83 2 2 2 t 25 C Rh2(OAc)4 600 Bu 82 Reactivity using Rh2(OAc)4 (Rh(II)) was higher than Rh(I), Rh(III). Rh2(OAc)4 600 H 80 Rh2(OAc)4 600 Ac 93 RhCl3•3H2O 125 Et 64 t RhCl3•3H2O 125 Bu 58 RhCl(PPh3)3 125 Et 49 2/17 2. Rhodium Carbenoid Induced Reaction 2-1. C-H Insertion ref.) Yamaguchi's Lit (M1 Part) Trend in Selectivity In simple case, Reactivity is determined with both electric effect and steric effect. D. F. Taver et al., JACS, 1986, 108, 7686. O O O R1 CO Et Rh (OAc) 1 2 3 2 2 4 CO Et CO Et R = Me, R = Me, R = Me (3 vs 2 ) 23 : 1 R3 2 R1 2 2 1 1 2 3 t R N2 R R = Me, R = H, R = Bu (2 vs 2 bulky) 34 : 1 R2 R2 R3 steric effect R3 tertially > secondary > primary (electric effect; electron density in the C-H bond) G. Stork et al., TL, 1988, 29, 2283. O O COCHN2 Rh (OAc) COCHN2 Rh2(OAc)4 2 4 CO Me CO2Et 2 CH2Cl2 (0.01 M) CO Me CH2Cl2 (0.01 M) CO2Et 2 rt rt 81% 0% dimer : 33% O COCHN2 Rh2(OAc)4 O COCHN2 Rh2(OAc)4 CH2Cl2 (0.01 M) CO2Me rt CO2Me CH2Cl2 (0.01 M) CO2Me 64% rt CO2Me 0% • electron-withdrawing groups inhibit adjacent C-H bond dimer : 31% Mechanism M. P. Doyle et al., JACS, 1993, 115, 958. D. F. Taber et al., JACS, 1996, 118, 547. C-Rh-Rh is 180 from calculation. They didn't perfom DFT calculation, but they expected from alined ligand (L) effect of C-H insertion. This mechanism was expected from experiments results, low EWG : general selectivity and ZINDO calculation was performed to ylide intermediate. high EWG : selectivity is decreased (attack low steric barrier) These mechanisms were plausible and widely accepted, but additional analysis of mechanism was performed for further development of the C-H activation chemistry. Proposed mechanism from DFT calculation E. Nakamura et al., JACS, 2002, 124, 7181. DFT using B3LYP on Rh2(O2CR)4 C-H activation/C-C bond formation reaction. calclated for [Rh2(O2CH)4 - CH2N2 - metane or propane] and [Rh2(O2CH)4 -N2CHCO2Et - metane or propane] 2 -Donation • carboxylate groups serves as anchors of the Rh atom • electron-withdrawing group (E) enhances the electrophilicity of the carbene carbon center • Rh1 has positive charge which increases the electrophilicity Rh2 Rh1 Rh Carbenoid of carbon center Formation • electron donation from Rh2 to Rh1 assist the C-C bond formation and catalyst regeneration. • If chiral ligand was used, it also serves as the site to harness chirarity. C-H Activation Activated energy is decreased, so C-H Insertion is enhanced. C-H Insertion compared to Cu-carbenoid and Ru-carbenoid, energy of C-H insertion to carbenoid is lower (diazomethane-methane). Dissociation H of NH Rh-Catalyst Cl O H H N Ru Cu (HCO2)4Rh2 CH2 C-C Bond H H Cl O Formation NH H 27.6 kcal/mol > 15.6 kcal/mol > 5.7 kcal/mol 3/17 Stereo-/Chemo-Selective Reaction Review; H. M. L. Davies et al., Chem. Rev., 2003, 103, 2861. H. M. L. Davies, ACIE, 2006, 45, 6422. Intramolecular reaction H. M. L. Davies et al., Nature, 2008, 451, 417. H. M. L. Davies et al., Chem. Soc. Rev., 2009, 38, 3061. M. P. Doyle et al., JACS, 1996, 118, 8837. M. P. Doyle et al., JOC, 2005, 70, 5291. 1.0 mol% I II Rh2(OAc)4 10 7 Rh2(4S-MPPIM)4 53 19 Rh2(5S-MEPY)4 62 23 Rh2(4S-MEOX)4 87 trace Rh2(4S-MPPIM)4 Rh2(5S-MEPY)4 Rh2(4S-MEOX)4 In this type reaction, it was thought that Rh-carbenoid reacts with equatrial C-H, because access to axial C-H is prevented by crowding of the cyclohexane ring.
Recommended publications
  • Treatise on Combined Metalworking Techniques: Forged Elements and Chased Raised Shapes Bonnie Gallagher
    Rochester Institute of Technology RIT Scholar Works Theses Thesis/Dissertation Collections 1972 Treatise on combined metalworking techniques: forged elements and chased raised shapes Bonnie Gallagher Follow this and additional works at: http://scholarworks.rit.edu/theses Recommended Citation Gallagher, Bonnie, "Treatise on combined metalworking techniques: forged elements and chased raised shapes" (1972). Thesis. Rochester Institute of Technology. Accessed from This Thesis is brought to you for free and open access by the Thesis/Dissertation Collections at RIT Scholar Works. It has been accepted for inclusion in Theses by an authorized administrator of RIT Scholar Works. For more information, please contact [email protected]. TREATISE ON COMBINED METALWORKING TECHNIQUES i FORGED ELEMENTS AND CHASED RAISED SHAPES TREATISE ON. COMBINED METALWORKING TECHNIQUES t FORGED ELEMENTS AND CHASED RAISED SHAPES BONNIE JEANNE GALLAGHER CANDIDATE FOR THE MASTER OF FINE ARTS IN THE COLLEGE OF FINE AND APPLIED ARTS OF THE ROCHESTER INSTITUTE OF TECHNOLOGY AUGUST ( 1972 ADVISOR: HANS CHRISTENSEN t " ^ <bV DEDICATION FORM MUST GIVE FORTH THE SPIRIT FORM IS THE MANNER IN WHICH THE SPIRIT IS EXPRESSED ELIEL SAARINAN IN MEMORY OF MY FATHER, WHO LONGED FOR HIS CHILDREN TO HAVE THE OPPORTUNITY TO HAVE THE EDUCATION HE NEVER HAD THE FORTUNE TO OBTAIN. vi PREFACE Although the processes of raising, forging, and chasing of metal have been covered in most technical books, to date there is no major source which deals with the functional and aesthetic requirements
    [Show full text]
  • Repoussé Work for Amateurs
    rf Bi oN? ^ ^ iTION av op OCT i 3 f943 2 MAY 8 1933 DEC 3 1938 MAY 6 id i 28 dec j o m? Digitized by the Internet Archive in 2011 with funding from Boston Public Library http://www.archive.org/details/repoussworkforamOOhasl GROUP OF LEAVES. Repousse Work for Amateurs. : REPOUSSE WORK FOR AMATEURS: BEING THE ART OF ORNAMENTING THIN METAL WITH RAISED FIGURES. tfjLd*- 6 By L. L. HASLOPE. ILLUSTRATED. LONDON L. UPCOTT GILL, 170, STRAND, W.C, 1887. PRINTED BY A. BRADLEY, 170, STRAND, LONDON. 3W PREFACE. " JjJjtfN these days, when of making books there is no end," ^*^ and every description of work, whether professional or amateur, has a literature of its own, it is strange that scarcely anything should have been written on the fascinating arts of Chasing and Repousse Work. It is true that a few articles have appeared in various periodicals on the subject, but with scarcely an exception they treated only of Working on Wood, and the directions given were generally crude and imperfect. This is the more surprising when we consider how fashionable Repousse Work has become of late years, both here and in America; indeed, in the latter country, "Do you pound brass ? " is said to be a very common question. I have written the following pages in the hope that they might, in some measure, supply a want, and prove of service to my brother amateurs. It has been hinted to me that some of my chapters are rather "advanced;" in other words, that I have gone farther than amateurs are likely to follow me.
    [Show full text]
  • Metals and Metal Products Tariff Schedules of the United States
    251 SCHEDULE 6. - METALS AND METAL PRODUCTS TARIFF SCHEDULES OF THE UNITED STATES SCHEDULE 6. - METALS AND METAL PRODUCTS 252 Part 1 - Metal-Bearing Ores and Other Metal-Bearing Schedule 6 headnotes: Materials 1, This schedule does not cover — Part 2 Metals, Their Alloys, and Their Basic Shapes and Forms (II chemical elements (except thorium and uranium) and isotopes which are usefully radioactive (see A. Precious Metals part I3B of schedule 4); B. Iron or Steel (II) the alkali metals. I.e., cesium, lithium, potas­ C. Copper sium, rubidium, and sodium (see part 2A of sched­ D. Aluminum ule 4); or E. Nickel (lii) certain articles and parts thereof, of metal, F. Tin provided for in schedule 7 and elsewhere. G. Lead 2. For the purposes of the tariff schedules, unless the H. Zinc context requires otherwise — J. Beryllium, Columbium, Germanium, Hafnium, (a) the term "precious metal" embraces gold, silver, Indium, Magnesium, Molybdenum, Rhenium, platinum and other metals of the platinum group (iridium, Tantalum, Titanium, Tungsten, Uranium, osmium, palladium, rhodium, and ruthenium), and precious- and Zirconium metaI a Iloys; K, Other Base Metals (b) the term "base metal" embraces aluminum, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, calcium, chromium, cobalt, columbium, copper, gallium, germanium, Part 3 Metal Products hafnium, indium, iron, lead, magnesium, manganese, mercury, A. Metallic Containers molybdenum, nickel, rhenium, the rare-earth metals (Including B. Wire Cordage; Wire Screen, Netting and scandium and yttrium), selenium, silicon, strontium, tantalum, Fencing; Bale Ties tellurium, thallium, thorium, tin, titanium, tungsten, urani­ C. Metal Leaf and FoU; Metallics um, vanadium, zinc, and zirconium, and base-metal alloys; D, Nails, Screws, Bolts, and Other Fasteners; (c) the term "meta I" embraces precious metals, base Locks, Builders' Hardware; Furniture, metals, and their alloys; and Luggage, and Saddlery Hardware (d) in determining which of two or more equally specific provisions for articles "of iron or steel", "of copper", E.
    [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]
  • Electrooxidation Enables Highly Regioselective Dearomative Annulation of Indole and Benzofuran Derivatives
    ARTICLE https://doi.org/10.1038/s41467-019-13829-4 OPEN Electrooxidation enables highly regioselective dearomative annulation of indole and benzofuran derivatives Kun Liu1, Wenxu Song1, Yuqi Deng1, Huiyue Yang1, Chunlan Song1, Takfaoui Abdelilah1, Shengchun Wang 1, Hengjiang Cong 1, Shan Tang1 & Aiwen Lei1* 1234567890():,; The dearomatization of arenes represents a powerful synthetic methodology to provide three-dimensional chemicals of high added value. Here we report a general and practical protocol for regioselective dearomative annulation of indole and benzofuran derivatives in an electrochemical way. Under undivided electrolytic conditions, a series of highly functio- nalized five to eight-membered heterocycle-2,3-fused indolines and dihydrobenzofurans, which are typically unattainable under thermal conditions, can be successfully accessed in high yield with excellent regio- and stereo-selectivity. This transformation can also tolerate a wide range of functional groups and achieve good efficiency in large-scale synthesis under oxidant-free conditions. In addition, cyclic voltammetry, electron paramagnetic resonance (EPR) and kinetic studies indicate that the dehydrogenative dearomatization annulations arise from the anodic oxidation of indole into indole radical cation, and this process is the rate- determining step. 1 College of Chemistry and Molecular Sciences, Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, P. R. China. *email: aiwenlei@whu. edu.cn NATURE COMMUNICATIONS | (2020) 11:3 | https://doi.org/10.1038/s41467-019-13829-4 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-019-13829-4 reaking the aromatic systems of electron-rich arenes or fused indolines (Fig. 1a)39–44. Therefore, it is highly appealing to heteroarenes provides three-dimensional chemicals of high develop efficient approaches to allow for their preparation.
    [Show full text]
  • PARASITES PREDATORS and SYMBIONTS a Thesis Submitted To
    PARASITES PREDATORS AND SYMBIONTS A thesis submitted to the College of the Arts of Kent State University in partial fulfillment of the requirements for the degree of Master of Fine Arts By Jody L. Vankeuren May 2021 Thesis written by Jody L. Vankeuren B.F.A., Edinboro University of Pennsylvania, 2018 M.F.A., Kent State University, 2021 Approved by Andrew Kuebeck, M.F.A., Advisor Marie Buukowski, M.F.A., Director, School of Art John R. Crawford- Spinelli, Ed.D., Dean, College of the Arts TABLE OF CONTENTS Page LIST OF FIGURES ......................................................................................................................................................... IV AKNOWLEDGEMENTS ............................................................................................................................................. V CHAPTER 1. INTRODUCTION .................................................................................................................................................. 1 2. RESEARCH ............................................................................................................................................................. 1 3. PARASITES PREDATORS AND SYMBIONTS- INDIVIDUAL WORKS ............................................. 4 4. INSTALATION ...................................................................................................................................................... 8 5. CONCLUSION .......................................................................................................................................................
    [Show full text]
  • Rhodium Roles Lars Öhrström Relates the Various Roles Played by Rhodium in Our Daily Lives, Ranging from Car Components to Drugs
    in your element Rhodium roles Lars Öhrström relates the various roles played by rhodium in our daily lives, ranging from car components to drugs. nce the thin electroplated rhodium information to be extracted by 2D NMR coating that makes new pieces spectroscopy techniques. Oof jewellery extra bright and Several artificial radioactive isotopes are shiny wears off, most of us are likely to also known, including meta-stable nuclear come across rhodium mainly as a crucial isomers. One of those, 103mRh — produced component in catalytic converters for by decay from 103Ru — has been investigated cars. In these devices, metallic particles of as a cancer therapy agent2. In light of its element 45 are embedded in the porous short half-life (59 min) and the slow ligand ceramic structure of the catalyst, and its exchange rates for Rh(iii) complexes, specific role is to help break down nitrogen however, the synthesis and use of 103mRh oxides to innocuous O2 and N2. compounds require careful planning. 4+ In 1988, a year before catalytic converters A variety of complexes based on the Rh2 became compulsory for new cars in Sweden, core have also shown promise as anticancer I encountered this otherwise silver-white compounds. Recently, in an exciting noble metal in a very different form: development, a dirhodium(ii) compound 50 grams of a purple powder, worth half a featuring a ligand endowed with an organic year’s pay for a graduate student. This price 3, ACS REF. FROM REPRODUCED fluorophore has been shown to be taken up reflected both the fact that element 45 is for applications, and the reason behind by cancer cells in a different manner than the typically the most expensive of the platinum William S.
    [Show full text]
  • Carbene and Nitrene Transfer Reactions Joseph B
    University of South Florida Scholar Commons Graduate Theses and Dissertations Graduate School 11-19-2014 Co(II) Based Metalloradical Catalysis: Carbene and Nitrene Transfer Reactions Joseph B. Gill University of South Florida, [email protected] Follow this and additional works at: https://scholarcommons.usf.edu/etd Part of the Organic Chemistry Commons Scholar Commons Citation Gill, Joseph B., "Co(II) Based Metalloradical Catalysis: Carbene and Nitrene Transfer Reactions" (2014). Graduate Theses and Dissertations. https://scholarcommons.usf.edu/etd/5484 This Dissertation is brought to you for free and open access by the Graduate School at Scholar Commons. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. Co(II) Based Metalloradical Catalysis: Carbene and Nitrene Transfer Reactions by Joseph B. Gill A dissertation in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: X. Peter Zhang, Ph.D. Jon Antilla, Ph.D Jianfeng Cai, Ph.D. Edward Turos, Ph.D. Date of Approval: November 19, 2014 Keywords: cyclopropanation, diazoacetate, azide, porphyrin, cobalt. Copyright © 2014, Joseph B. Gill Dedication I dedicate this work to my parents: Larry and Karen, siblings: Jason and Jessica, and my partner: Darnell, for their constant support. Without all of you I would never have made it through this journey. Thank you. Acknowledgments I would like to thank my advisor, Professor X. Peter Zhang, for his support and guidance throughout my time working with him.
    [Show full text]
  • 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.
    [Show full text]
  • Organic Synthesis: New Vistas in the Brazilian Landscape
    Anais da Academia Brasileira de Ciências (2018) 90(1 Suppl. 1): 895-941 (Annals of the Brazilian Academy of Sciences) Printed version ISSN 0001-3765 / Online version ISSN 1678-2690 http://dx.doi.org/10.1590/0001-3765201820170564 www.scielo.br/aabc | www.fb.com/aabcjournal Organic Synthesis: New Vistas in the Brazilian Landscape RONALDO A. PILLI and FRANCISCO F. DE ASSIS Instituto de Química, UNICAMP, Rua José de Castro, s/n, 13083-970 Campinas, SP, Brazil Manuscript received on September 11, 2017; accepted for publication on December 29, 2017 ABSTRACT In this overview, we present our analysis of the future of organic synthesis in Brazil, a highly innovative and strategic area of research which underpins our social and economical progress. Several different topics (automation, catalysis, green chemistry, scalability, methodological studies and total syntheses) were considered to hold promise for the future advance of chemical sciences in Brazil. In order to put it in perspective, contributions from Brazilian laboratories were selected by the citations received and importance for the field and were benchmarked against some of the most important results disclosed by authors worldwide. The picture that emerged reveals a thriving area of research, with new generations of well-trained and productive chemists engaged particularly in the areas of green chemistry and catalysis. In order to fulfill the promise of delivering more efficient and sustainable processes, an integration of the academic and industrial research agendas is to be expected. On the other hand, academic research in automation of chemical processes, a well established topic of investigation in industrial settings, has just recently began in Brazil and more academic laboratories are lining up to contribute.
    [Show full text]
  • And Intermolecular Cyclopropanation by Co(II)- Based Metalloradical Catalysis Xue Xu University of South Florida, [email protected]
    University of South Florida Scholar Commons Graduate Theses and Dissertations Graduate School January 2012 Asymmetric Intra- and Intermolecular Cyclopropanation by Co(II)- Based Metalloradical Catalysis Xue Xu University of South Florida, [email protected] Follow this and additional works at: http://scholarcommons.usf.edu/etd Part of the American Studies Commons, and the Organic Chemistry Commons Scholar Commons Citation Xu, Xue, "Asymmetric Intra- and Intermolecular Cyclopropanation by Co(II)- Based Metalloradical Catalysis" (2012). Graduate Theses and Dissertations. http://scholarcommons.usf.edu/etd/4262 This Dissertation is brought to you for free and open access by the Graduate School at Scholar Commons. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. Asymmetric Intra- and Intermolecular Cyclopropanation by Co(II)- Based Metalloradical Catalysis by Xue(Snow) Xu A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: X. Peter Zhang, Ph.D. Jon Antilla, Ph.D. Mark L. McLaughlin, Ph.D. Wayne Guida, Ph.D. Date of Defense: June 20th, 2012 Keywords: cobalt, porphyrin, catalysis, cyclopropanation, carbene, diazo Copyright © 2012, Xue Xu DEDICATION I dedicate this dissertation to my parents and my husband, without their caring support, it would not have been possible. ACKNOWLEGEMENTS I need to begin with thanking Dr. Peter Zhang for his continuous guidance and support over the last 5 and half years. Especially for encouraging me to achieving my potential as a researcher and setting an example of dedication to science that is admirable.
    [Show full text]
  • Copper Alloys
    THE COPPER ADVANTAGE A Guide to Working With Copper and Copper Alloys www.antimicrobialcopper.com CONTENTS I. Introduction ............................. 3 PREFACE Conductivity .....................................4 Strength ..........................................4 The information in this guide includes an overview of the well- Formability ......................................4 known physical, mechanical and chemical properties of copper, Joining ...........................................4 as well as more recent scientific findings that show copper has Corrosion ........................................4 an intrinsic antimicrobial property. Working and finishing Copper is Antimicrobial ....................... 4 techniques, alloy families, coloration and other attributes are addressed, illustrating that copper and its alloys are so Color ..............................................5 adaptable that they can be used in a multitude of applications Copper Alloy Families .......................... 5 in almost every industry, from door handles to electrical circuitry to heat exchangers. II. Physical Properties ..................... 8 Copper’s malleability, machinability and conductivity have Properties ....................................... 8 made it a longtime favorite metal of manufacturers and Electrical & Thermal Conductivity ........... 8 engineers, but it is its antimicrobial property that will extend that popularity into the future. This guide describes that property and illustrates how it can benefit everything from III. Mechanical
    [Show full text]