Division of Organic Chemistry

Total Page:16

File Type:pdf, Size:1020Kb

Division of Organic Chemistry ORGN DIVISION OF ORGANIC CHEMISTRY S. Silverman and E. McLaughlin, Program Chairs SUNDAY MORNING Section A Pennsylvania Convention Center 116 New Reactions & Methodology S. M. Silverman, Organizer 8:00 1. Copper catalyzed reductive carbonylation of alkyl iodides. S. Zhao, N.P. Mankad 8:20 2. Sulfenate-anion-catalyzed diastereoselective aziridination of imines. Z. Zheng, P.J. Walsh 8:40 3. Cyanoalkylcopper species in carbon-carbon bond forming reactions. D.L. Silverio 9:00 4. New reactivity enabled by cation-π interactions. P.J. Walsh 9:20 5. Dipolar alkynyl-prins (DAP) cyclization for the rapid construction of complex polycycles. S. Abdul-Rashed, G. Alachouzos, A. Frontier 9:40 6. Subphthalocyanines and perylene-diimide derivatives in organic photovoltaics. L. Chockalingam Kasi Viswanath 10:00 7. Silylated α-aminonitriles for late-stage functionalization. T. Mathew, T. Yamato, S.G. Prakash 10:20 8. Synthesis of differentially substituted diynes via tandem nucleophilic addition/fragmentation pathways. A. Tavakoli, G.B. Dudley 10:40 9. Analogues of Bestmann’s ylide, Ph3P=C=C=O: Syntheses, structures and Lewis acid catalyzed cyclizations with organic substrates. C. Krempner 11:00 10. Diastereoselective alkynylations of β-(Bromo)iminium ions via copper(I) catalysis. S.O. Santana, W. Guan, M.P. Watson 11:20 11. Modular three-component difunctionalization of aryl/cyclohexenyl triflates via arynes and cyclohexynes. S. Cho, Q. Wang 11:40 12. 1,2-aminocyanation of alkenes via distal migration. Y. Kwon, Q. Wang Section B Pennsylvania Convention Center 117 Heterocycles & Aromatics S. M. Silverman, Organizer 8:00 13. Formal [4+2] cycloaddition between alkynes and allene-ynes to generate functionalized toluenes. A.D. Le, D. Lee, S. Gupta 8:20 14. Regioselective carbonylation of 2,2-disubstituted epoxides. A.K. Hubbell, J.R. Lamb, A.M. LaPointe, K. Klimovica, G.W. Coates 8:40 15. Cupper catalyzed N-arylation of 4-R-1,2,4-triazoles. J.L. Bolliger 9:00 16. Formation of tricyclic aromatic heterocycles mediated by oxidative disulfide coupling. J.L. Bolliger 9:20 17. New methods for aryl C-N and C-O bond formation using sequential iron and copper catalysis. M.C. Henry 9:40 18. Control of halogen dance and its application to the synthesis of substituted heteroaromatic compounds. K. Okano, S. Hirai, Y. Hayashi, K. Inoue, M. Aoki, A. Mori 10:00 19. Development of 2-pyridinyl-1,2,4-triazine alkoxy-substituted scaffolds for minor actinide separations. M.L. Tedder, J.D. Carrick 10:20 20. Convergent strategy for the synthesis of oxa-, thia-, and seleno[5]helicenes by acetylene-activated SNAr reactions. J.L. Katz, S. Hoenig, Y. Yan, E. Dougherty, S. Petovic, C. Lee, Y. Hu, L. Gomez 10:40 21. Synthesis of polycyclic spiro lignan natural product model substrates. G. Ali, G.D. Cuny 11:00 22. Para- and [4+4] photocycloadditions in mixed pyridone–benzene systems. L.M. Rossiter, S. Fletcher, B. Garas, S.M. Sieburth 11:20 23. Cyclopentannulation and cyclodehydrogenation of isomericaly pure 5,11- dibromoanthradithiophenes leading to contorted aromatics. W.a. Hussain 11:40 24. Diastereoselective synthesis of N-(hetero)aryl-piperidines. M.A. Larsen, A.C. Sather, M. Deem, E. Hennessy, J. Sauri, C. Lam Section C Pennsylvania Convention Center 120A Flow Chemistry & Continuous Processes S. M. Silverman, Organizer 9:00 25. Approaches to scaling-up linked continuous flow photo-, electro- and thermal- chemistry: New reactors and new approaches. M.W. George 9:30 26. "Machine-Assisted Synthesis: Programmable Precision Polymers by the Push of a Button". T. Junkers 10:00 27. Continuous plug flow antisolvent crystallization of active pharmaceutical ingredients. A.H. Bond, K. Nordquist, K. Schaab, S. Ferdous, T. Kinnibrugh, A. Thorat, G. Capellades, A.S. Myerson 10:30 28. Synthesis of substituted heteroarenes and their subsequent reduction using flow technology to produce novel heterocycles. G.V. Sipos, I.K. Varga, K. Bodroghy Section D Pennsylvania Convention Center 120B Contributions of Synthetic Chemistry to Energy Storage C. Sevov, S. Zhang, Organizers, Presiding 8:30 Introductory Remarks. 8:35 29. Synthetic control of stoichiometry, size, and defect distributions: Beneficial impact on resultant electrochemistry. K.J. Takeuchi, A.C. Marschilok, E.S. Takeuchi 9:05 30. Making new materials for energy storage. C.P. Nuckolls 9:35 31. Organic electrode material design for beyond lithium-ion batteries. Y. Yao 10:05 Intermission. 10:25 32. Diversity-oriented synthesis of new polymers for battery applications. B. Helms, M. Baran, M. Carrington, M. Baird, A.I. Baskin, D. Prendergast 10:55 33. Going a step beyond: Isolating and characterizing the charged states of active battery materials. S.A. Odom 11:25 34. Design strategies for organic solids and solutions in hybrid redox flow batteries. C.S. Sevov 11:55 Concluding Remarks. Section E Pennsylvania Convention Center 118A The Power of High-Throughput Experimentation: Accelerated Synthetic Development & New Reaction Discovery M. Jouffroy, Organizer M. Emmert, Organizer, Presiding M. Jouffroy, Presiding 9:00 Introductory Remarks. 9:05 35. Use of high-pressure and high-throughput experimentation, and theory to optimize the catalytic borylation of methane with well-defined iridium complexes. D.J. Mindiola 9:35 36. Utilizing high-throughput experimentation to catalyze diverse chemistry and collaborations within and outside of Merck. D.M. Schultz 10:05 37. Engaging esters, aldehydes, and alcohols in cross-coupling: High throughput approach to reaction discovery. S. Newman 10:35 38. Applications of HTE to the discovery and development of robust, scalable catalytic transformations for the synthesis of complex pharmaceutical intermediates. E. Simmons 11:05 39. High-throughput experimentation for the life sciences. T. Cernak Section F Pennsylvania Convention Center Michael A Nutter Theatre Carbon Allotropes, Materials, Devices & Switches Cosponsored by I&EC S. M. Silverman, Organizer 8:00 40. Aryl amphiphile shape-directors for the shape-controlled synthesis of organic semiconductor micro- and nano-crystals. D. Jones, N. Gavvalapalli 8:20 41. Light-driven chiral liquid crystal nanostructures enabled by chiral molecular switches or motors: Dynamic photonics. Q. Li 8:40 42. Bisphenalenyl Radical Salts and their Uniquely Open-shell Optoelectronic Properties. C.M. Wehrmann, M.S. Chen 9:00 43. Synthesis of [5]- and [7]-Carbohelicene through regioselective cyclodehydrogenation. Z. Qiu, A. Narita, K. Muellen 9:20 44. Evidence of orientational order in thiophene derived carbon nanothreads. A. Biswas, M. Ward, T. Wang, L. Zhu, H. Huang, J.V. Badding, V. Crespi, T.A. Strobel 9:40 45. Customizing the optoelectronic and chiroptical properties of carbon-based dots. M. Vázquez-Nakagawa, A. Ferrer-Ruiz, L. Rodríguez-Pérez, N. Martín, M. Herranz 10:00 46. Tubularenes: Redefining carbon-based nanotubes. E. Castro, S. Mirzaei, O. Abarbanel, R. Hernandez Sanchez 10:20 47. Nanocarbon morphology shapes hybrid functional matter. D. Iglesias, M. Melle- Franco, A. Beltram, S. Kralj, M. Melchionna, S. Marchesan 10:40 48. Tubular[n]arenes: Bottom-up approach to carbon-based nanotubes analogues. O. Abarbanel, E. Castro, S. Mirzaei, R. Hernandez Sanchez 11:00 49. Synthesis and polymerization of diynes containing thiocyanate and thiophene end- groups en route towards polydiacetylenes. R. DeCicco 11:20 50. Award Address (ACS Award for Creative Invention sponsored by the ACS Corporation Associates). Photochromism and its commercial application. A. Kumar SUNDAY AFTERNOON Section A Pennsylvania Convention Center 116 New Reactions & Methodology S. M. Silverman, Organizer J. Li, Presiding 1:00 51. Metal-free trifluoromethylation of phenols via xanthates: New synthesis of aryl and heteroaryl-trifluoromethyl ethers. A.T. Londregan, M. Yoritate, Y. Lian, J.F. Hartwig 1:20 52. Development of safer methods for cleavage of the Evans auxiliary. G. Beutner, D.D. Dixon, E. Lo, J.M. Stevens 1:40 53. New strategies toward catalytic alkene dicarbofunctionalization. R. Giri 2:00 54. Sequencing [4+1]-cycloaddition and aza-Michael addition reactions: Tandem cascades for the rapid and modular access of unique collections of anticancer and anti-superbugs motifs. T.H. Altel, S. Vunnam 2:20 55. Synthesis of 2,4'-bipyridines via a unique radical coupling of cyanopyridines and heteroaryl phosphonium salts. J.W. Greenwood, J.L. Koniarczyk, J.V. Alegre-Requena, R.S. Paton, A. McNally 2:40 56. Regioselective nucleophilic substitution of the Baylis-Hillman (BH) adducts: Applications to the synthesis of heterocyclic derivatives. Z. Shafiq, L. Liu 3:00 57. Hindered urea bond: Bilaterally responsive chemistry to hydrogen peroxide. Y. Yang, H. Ying, J. Cheng 3:20 58. Shedding new light on squaraines: Utilizing squaraine dyes as building blocks in organic synthesis. E. Bacher, B.L. Ashfeld 3:40 59. Photochemical synthesis of bicyclic amines for drug discovery. P. Mykhailiuk, A. Denisenko, Y. Skalenko, A. Kirichok, B. Chalyk, T. Druzhenko, D. Dibchak 4:00 60. Rapid access to functionalized trifluoromethyl-substituted aliphatic derivatives. P. Mykhailiuk, M. Bugera, S. Trofymchuk, K. Tarasenko, Y. Pustovit 4:20 61. Photoacid catalyzed C-C bond-formation: Synthesis of triarylmethanes and 3,3’- diarylindolin-2-ones. Z.M. Salem, J. Saway, J.J. Badillo 4:40 62. Direct decarboxylative functionalization of carboxylic acids via O–H hydrogen atom transfer. C.G. Na, E.J. Alexanian Section B Pennsylvania Convention Center 117 Biologically-Related Molecules & Processes S. M. Silverman, Organizer 1:00 63. Non-enzymatic synthesis of biologically important phosphates and polyphosphates. M. Perez-Ramirez, N. Zungpoih, B. Otoo 1:20 64. Chemical targeting of voltage sensitive dyes to specific cell types in the brain. T. Fiala, J. Wang, M. Dunn, S. Choi, P. Sebej, E.C. Nwadibia, E. Fialova, D.M. Martinez, D. Sulzer, D. Sames 1:40 65. BODIPY photocages: Structure-activity relationship in quantum yield of photorelease. P. Shrestha 2:00 66. Synthetic simplification of carolacton leads to identification of novel biofilm target. A.E. Solinski, A. Scharnow, A.J. Fraboni, E. Shaw, W.M. Wuest 2:20 67. Unusual ethyl branched chain fatty acids: Synthesis and biological evaluation.
Recommended publications
  • Appendix 1 Table of Contents
    @ECHA EUROPEAN CHEMICALS AGENCY Appendix 1 Table of Contents: Supplementary Table C:Substances on Annex II of the Cosmetic Products Regulation ... 1 Supplementary Table D: Substances proposed to be restricted due their use restriction in CPR Annex IV column 9..,,.. 119 Supplementary Table E: Substances allowed in tattoo inks subject to the conditions specified in CPR Annex IV columns h and i ......r29 Annankatu 18. P.O. Box 400, FI-00121 Helsinki, Finland I Tel. +358 9 686180 | Fax +358 9 68618210 | echa.europa.eu ANNEX XV RESTRICTION REPORT - SUBSTANCES IN TATTOO INKS AND PERMANENT MAKE UP Su lemen Table C:Substances on Annex II of the Cosmetic Products Re ulationl Substance EC# cAs # Substance EC# cAs # R T T T A- s c R I T Name Name e b b b II s M 7 c I s I I I #4 5 6 D 9 2 1 2 3 a 3 3 3 N-(s- Chlorobenzoxa zol-2- 35783- vl)acetamide 57-4 1 (2- Acetoxyethyl)t rimethylammo (2- nium acetoxyethyl hydroxide )trimethyla 200- (Acetylcholine) 200- mmonium 124-9 5 1-84-3 and its salts t2a-9 51-84-3 2 Deanol Deanol 222- 3342- aceglumate 222- 3342- aceqlumate 085-5 61-8 (INN) 085-5 61-8 3 Spironolacto 200- Spironolactone 200- ne 133-6 52-O1-7 rINN) 133-6 52-0L-7 4 14-(4- Hydroxy-3- iodophenoxy)- 3,5- diiodophenylla cetic acid (Tiratricol 200- (INN)) and its 200- Tiratricol 086- 1 5r-24-7 salts 086- 1 5l-24-7 5 Methotrexat 200- Methotrexate 200- e 413-8 59-05-2 (INN) 413-8 59-05-2 6 Aminocaproic Aminocaproi 200- acid (INN) and 200- c acid 469-3 60-32-2 its salts 469-3 60-32-2 7 Cinchophen (rNN), its salts, derivatives and salts of 205- 132-60- these 205- 132-60- Cinchophen 067-r 5 derivatives 067-l 5 Thyropropic acid (INN) and its salts 5L-26-3 9 Trichloroacet 200- Trichloroacetic 200- ic acid 927-2 75-03-9 acid 927-2 76-03-9 l0 Aconitum napellus L.
    [Show full text]
  • Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Ba
    University of Tennessee, Knoxville Trace: Tennessee Research and Creative Exchange Masters Theses Graduate School 12-2009 Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions Manpreet Kaur Cheema University of Tennessee - Knoxville Recommended Citation Cheema, Manpreet Kaur, "Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions. " Master's Thesis, University of Tennessee, 2009. https://trace.tennessee.edu/utk_gradthes/517 This Thesis is brought to you for free and open access by the Graduate School at Trace: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Masters Theses by an authorized administrator of Trace: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a thesis written by Manpreet Kaur Cheema entitled "Design and Synthesis of FRET-Based Boronic Acid Receptors to Detect Carbohydrate Clustering and Development of Diacylglycerol-Based Lipid Probesto Investigate Lipid-Protein Binding Interactions." I have examined the final electronic copy of this thesis for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of Master of Science, with a major in Chemistry. Michael Best, Major
    [Show full text]
  • Fluorescent Aminal Linked Porous Organic Polymer for Reversible Iodine Capture and Sensing Muhammad A
    www.nature.com/scientificreports OPEN Fluorescent aminal linked porous organic polymer for reversible iodine capture and sensing Muhammad A. Sabri1, Mohammad H. Al‑Sayah2, Susan Sen2, Taleb H. Ibrahim1 & Oussama M. El‑Kadri2* A novel triazene-anthracene-based fuorescent aminal linked porous organic polymer (TALPOP) was prepared via metal free-Schif base polycondensation reaction of 9,10-bis-(4,6-diamino-S‑triazin‑ 2-yl)anthracene and 2-furaldehyde. The polymer has exceptional chemical and thermal stabilities and exhibit good porosity with Brunauer–Emmett–Teller surface area of 401 m2g−1. The combination of such porosity along with the highly conjugated heteroatom-rich framework enabled the polymer to exhibit exceptional iodine vapor uptake of up to 314 wt % and reversible iodine adsorption in solution. Because of the inclusion of the anthracene moieties, the TALPOP exhibited excellent 3 −1 detection sensitivity towards iodine via forescence quenching with Ksv value of 2.9 × 10 L mol . The cost efective TALPOP along with its high uptake and sensing of iodine, make it an ideal material for environmental remediation. Nuclear energy is becoming one of the most feasible alternative sources to meet the ever-increasing energy demand and minimize the emission of greenhouse gases because of its high-density energy, minimal carbon footprints, and low operation cost1–4. Despite such advantages, the potential emissions of radioactive material 129 131 3 14 85 (such as I and I, H, CO2, and Kr) from nuclear energy power plants is a major drawback of this tech- nology due to the serious environmental and health efect of these materials4,5.
    [Show full text]
  • Bottom-Up Synthesis and Sensor Applications of Biomimetic Nanostructures
    materials Review Bottom-Up Synthesis and Sensor Applications of Biomimetic Nanostructures Li Wang 1,*, Yujing Sun 2, Zhuang Li 2, Aiguo Wu 3 and Gang Wei 4,* Received: 25 November 2015; Accepted: 7 January 2016; Published: 18 January 2016 Academic Editor: Erik Reimhult 1 College of Chemistry, Jilin Normal University, Haifeng Street 1301, Siping 136000, China 2 State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5625, Changchun 130022, China; [email protected] (Y.S.); [email protected] (Z.L.) 3 Key Laboratory of Magnetic Materials and Devices & Division of Functional Materials and Nanodevices, Ningbo Institute of Material Technology and Engineering, Chinese Academy Sciences, Ningbo 315201, China; [email protected] 4 Faculty of Production Engineering, University of Bremen, Am Fallturm 1, D-28359 Bremen, Germany * Correspondence: [email protected] (L.W.); [email protected] (G.W.); Tel.: +86-139-4441-1011 (L.W.); +49-421-2186-4581 (G.W.) Abstract: The combination of nanotechnology, biology, and bioengineering greatly improved the developments of nanomaterials with unique functions and properties. Biomolecules as the nanoscale building blocks play very important roles for the final formation of functional nanostructures. Many kinds of novel nanostructures have been created by using the bioinspired self-assembly and subsequent binding with various nanoparticles. In this review, we summarized the studies on the fabrications and sensor applications of biomimetic nanostructures. The strategies for creating different bottom-up nanostructures by using biomolecules like DNA, protein, peptide, and virus, as well as microorganisms like bacteria and plant leaf are introduced.
    [Show full text]
  • Vibration Control of Diamond Nanothreads by Lattice Defect Introduction for Application in Nanomechanical Sensors
    nanomaterials Article Vibration Control of Diamond Nanothreads by Lattice Defect Introduction for Application in Nanomechanical Sensors Xiao-Wen Lei 1,* , Kazuki Bando 1 and Jin-Xing Shi 2 1 Department of Mechanical Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 910-8507, Japan; [email protected] 2 Department of Production Systems Engineering and Sciences, Komatsu University, Nu 1-3 Shicyomachi, Komatsu 923-8511, Japan; [email protected] * Correspondence: [email protected]; Tel.: +81-776-27-8544 Abstract: Carbon nanomaterials, such as carbon nanotubes (CNTs) and graphene sheets (GSs), have been adopted as resonators in vibration-based nanomechanical sensors because of their extremely high stiffness and small size. Diamond nanothreads (DNTs) are a new class of one-dimensional carbon nanomaterials with extraordinary physical and chemical properties. Their structures are similar to that of diamond in that they possess sp3-bonds formed by a covalent interaction between multiple benzene molecules. In this study, we focus on investigating the mechanical properties and vibration behaviors of DNTs with and without lattice defects and examine the influence of density and configuration of lattice defects on the two them in detail, using the molecular dynamics method and a continuum mechanics approach. We find that Young’s modulus and the natural frequency can be controlled by alternating the density of the lattice defects. Furthermore, we investigate and explore the use of DNTs as resonators in nanosensors. It is shown that applying an additional extremely small Citation: Lei, X.-W.; Bando, K.; mass or strain to all types of DNTs significantly changes their resonance frequencies.
    [Show full text]
  • The First General Electron Transfer Reductions of Carboxylic Acid Derivatives Using Samarium Diiodide
    The First General Electron Transfer Reductions of Carboxylic Acid Derivatives Using Samarium Diiodide A thesis submitted to The University of Manchester for the degree of Doctor of Philosophy In the faculty of Engineering and Physical Sciences 2014 Malcolm Peter Spain School of Chemistry Malcolm Spain PhD Thesis Contents Abstract .................................................................................................................... 5 Declaration................................................................................................................ 6 Copyright statement .................................................................................................. 7 Acknowledgements ................................................................................................... 9 Abbreviations .......................................................................................................... 10 Chapter 1. Introduction ........................................................................................... 13 1.1 Introduction to samarium diiodide .................................................................. 13 1.2 Reduction of ketones and aldehydes ............................................................. 15 1.3 Reduction of carboxylic acid derivatives ....................................................... 23 Chapter 2. Investigations of the SmI2–H2O system ................................................. 27 2.0 Preliminary studies of the SmI2–H2O system ................................................
    [Show full text]
  • Enantioselective Total Synthesis of (-)-Deoxoapodine
    Enantioselective total synthesis of (-)-deoxoapodine The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Kang, Taek, et al., "Enantioselective total synthesis of (-)- deoxoapodine." Angewandte Chemie International Edition 56, 44 (Sept. 2017): p. 13857-60 doi 10.1002/anie.201708088 ©2017 Author(s) As Published 10.1002/anie.201708088 Publisher Wiley Version Author's final manuscript Citable link https://hdl.handle.net/1721.1/125957 Terms of Use Creative Commons Attribution-Noncommercial-Share Alike Detailed Terms http://creativecommons.org/licenses/by-nc-sa/4.0/ HHS Public Access Author manuscript Author ManuscriptAuthor Manuscript Author Angew Manuscript Author Chem Int Ed Engl Manuscript Author . Author manuscript; available in PMC 2018 October 23. Published in final edited form as: Angew Chem Int Ed Engl. 2017 October 23; 56(44): 13857–13860. doi:10.1002/anie.201708088. Enantioselective Total Synthesis of (−)-Deoxoapodine Dr. Taek Kang§,a, Dr. Kolby L. White§,a, Tyler J. Mannb, Prof. Dr. Amir H. Hoveydab, and Prof. Dr. Mohammad Movassaghia aDepartment of Chemistry, Massachusetts Institute of Technology Cambridge, MA 02139 (USA) bDepartment of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467 (USA) Abstract The first enantioselective total synthesis of (−)-deoxoapodine is described. Our synthesis of this hexacyclic aspidosperma alkaloid includes an efficient molybdenum-catalyzed enantioselective ring-closing metathesis reaction for desymmetrization of an advanced intermediate that introduces the C5-quaternary stereocenter. After C21-oxygenation, the pentacyclic core was accessed via an electrophilic C19-amide activation and transannular spirocyclization. A biogenetically inspired dehydrative C6-etherification reaction proved highly effective to secure the F-ring and the fourth contiguous stereocenter of (−)-deoxoapodine with complete stereochemical control.
    [Show full text]
  • Synthesis and Structural Studies of a New Class of Quaternary Ammonium
    Rivera et al. Chemistry Central Journal 2011, 5:55 http://journal.chemistrycentral.com/content/5/1/55 RESEARCHARTICLE Open Access Synthesis and structural studies of a new class of quaternary ammonium salts, which are derivatives of cage adamanzane type aminal 1, 3, 6, 8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) Augusto Rivera1*, John Sadat-Bernal1, Jaime Ríos-Motta1, Michal Dušek2 and Lukáš Palatinus2 Abstract Background: Novel mono N-alkyl quaternary ammonium salts (3a-f) were prepared using the Menschutkin reaction from the cage adamanzane type aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (TATU) and alkyl iodides, such as methyl, ethyl, propyl, butyl, pentyl and hexyl iodide (2a-f), in dry acetonitrile at room temperature. Results: The structures of these new quaternary ammonium salts were established using various spectral and electrospray ionization mass spectrometry (ESI-MS) analyses. Compound (3b) was also analyzed using X-ray crystallography. Conclusion: It was noted that alkyl chain length did not significantly affect the reaction because all employed alkyl iodide electrophiles reacted in a similar fashion with the aminal 1 to produce the corresponding mono N- quaternary ammonium salts, which were characterized by spectroscopic and analytical techniques. Background amines with haloalkyls [7]. We found that no reaction Cage aminals of the adamanzane type are tricyclic ter- occurred when N-alkylation was attempted using alkyl tiary tetraamines, which can act as bases or as nucleo- bromides and chlorides. Compound 1 reacts with alkyl philes. The main subject of research in our laboratory iodides in dry acetonitrile at room temperature to pro- (Universidad Nacional, Bogotá) is the reactivity of these duce mono N-alkyl ammonium quaternary salts (3a-f) polyamine bases toward nucleophiles and electrophiles.
    [Show full text]
  • Reductions and Reducing Agents
    REDUCTIONS AND REDUCING AGENTS 1 Reductions and Reducing Agents • Basic definition of reduction: Addition of hydrogen or removal of oxygen • Addition of electrons 9:45 AM 2 Reducible Functional Groups 9:45 AM 3 Categories of Common Reducing Agents 9:45 AM 4 Relative Reactivity of Nucleophiles at the Reducible Functional Groups In the absence of any secondary interactions, the carbonyl compounds exhibit the following order of reactivity at the carbonyl This order may however be reversed in the presence of unique secondary interactions inherent in the molecule; interactions that may 9:45 AM be activated by some property of the reacting partner 5 Common Reducing Agents (Borohydrides) Reduction of Amides to Amines 9:45 AM 6 Common Reducing Agents (Borohydrides) Reduction of Carboxylic Acids to Primary Alcohols O 3 R CO2H + BH3 R O B + 3 H 3 2 Acyloxyborane 9:45 AM 7 Common Reducing Agents (Sodium Borohydride) The reductions with NaBH4 are commonly carried out in EtOH (Serving as a protic solvent) Note that nucleophilic attack occurs from the least hindered face of the 8 carbonyl Common Reducing Agents (Lithium Borohydride) The reductions with LiBH4 are commonly carried out in THF or ether Note that nucleophilic attack occurs from the least hindered face of the 9:45 AM 9 carbonyl. Common Reducing Agents (Borohydrides) The Influence of Metal Cations on Reactivity As a result of the differences in reactivity between sodium borohydride and lithium borohydride, chemoselectivity of reduction can be achieved by a judicious choice of reducing agent. 9:45 AM 10 Common Reducing Agents (Sodium Cyanoborohydride) 9:45 AM 11 Common Reducing Agents (Reductive Amination with Sodium Cyanoborohydride) 9:45 AM 12 Lithium Aluminium Hydride Lithium aluminiumhydride reacts the same way as lithium borohydride.
    [Show full text]
  • Course Material 2.Pdf
    Reactive Intermediates Source: https://www.askiitians.com/iit-jee-chemistry/organic-chemistry/iupac- and-goc/reaction-intermediates/ Table of Content • Carbocations • Carbanions • Free Radicals • Carbenes • Arenium Ions • Benzynes Synthetic intermediate are stable products which are prepared, isolated and purified and subsequently used as starting materials in a synthetic sequence. Reactive intermediate, on the other hand, are short lived and their importance lies in the assignment of reaction mechanisms on the pathway from the starting substrate to stable products. These reactive intermediates are not isolated, but are detected by spectroscopic methods, or trapped chemically or their presence is confirmed by indirect evidence. • Carbocations Carbocations are the key intermediates in several reactions and particularly in nucleophilic substitution reactions. Structure of Carbocations : Generally, in the carbocations the positively charged carbon atom is bonded to three other atoms and has no nonbonding electrons. It is sp 2 hybridized with a planar structure and bond angles of about 120°. There is a + vacant unhybridized p orbital which in the case of CH 3 lies perpendicular to the plane of C—H bonds. Stability of Carbocations: There is an increase in carbocation stability with additional alkyl substitution. Thus one finds that addition of HX to three typical olefins decreases in the order (CH 3)2C=CH 2>CH 3—CH = CH 2 > CH 2 = CH 2. This is due to the relative stabilities of the carbocations formed in the rate determining step which in turn follows from the fact that the stability is increased by the electron releasing methyl group (+I), three such groups being more effective than two, and two more effective than one.
    [Show full text]
  • 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G
    j1 1 Structure, Properties, and Preparation of Boronic Acid Derivatives Overview of Their Reactions and Applications Dennis G. Hall 1.1 Introduction and Historical Background Structurally, boronic acids are trivalent boron-containing organic compounds that possess one carbon-based substituent (i.e., a CÀB bond) and two hydroxyl groups to fill the remaining valences on the boron atom (Figure 1.1). With only six valence electrons and a consequent deficiency of two electrons, the sp2-hybridized boron atom possesses a vacant p-orbital. This low-energy orbital is orthogonal to the three substituents, which are oriented in a trigonal planar geometry. Unlike carbox- ylic acids, their carbon analogues, boronic acids, are not found in nature. These abiotic compounds are derived synthetically from primary sources of boron such as boric acid, which is made by the acidification of borax with carbon dioxide. Borate esters, one of the key precursors of boronic acid derivatives, are made by simple dehydration of boric acid with alcohols. The first preparation and isolation of a boronic acid was reported by Frankland in 1860 [1]. By treating diethylzinc with triethylborate, the highly air-sensitive triethylborane was obtained, and its slow oxidation in ambient air eventually provided ethylboronic acid. Boronic acids are the products of a twofold oxidation of boranes. Their stability to atmospheric oxidation is considerably superior to that of borinic acids, which result from the first oxidation of boranes. The product of a third oxidation of boranes, boric acid, is a very stable and relatively benign compound to humans (Section 1.2.2.3). Their unique properties and reactivity as mild organic Lewis acids, coupled with their stability and ease of handling, are what make boronic acids a particularly attractive class of synthetic intermediates.
    [Show full text]
  • Reactions of Benzene & Its Derivatives
    Organic Lecture Series ReactionsReactions ofof BenzeneBenzene && ItsIts DerivativesDerivatives Chapter 22 1 Organic Lecture Series Reactions of Benzene The most characteristic reaction of aromatic compounds is substitution at a ring carbon: Halogenation: FeCl3 H + Cl2 Cl + HCl Chlorobenzene Nitration: H2 SO4 HNO+ HNO3 2 + H2 O Nitrobenzene 2 Organic Lecture Series Reactions of Benzene Sulfonation: H 2 SO4 HSO+ SO3 3 H Benzenesulfonic acid Alkylation: AlX3 H + RX R + HX An alkylbenzene Acylation: O O AlX H + RCX 3 CR + HX An acylbenzene 3 Organic Lecture Series Carbon-Carbon Bond Formations: R RCl AlCl3 Arenes Alkylbenzenes 4 Organic Lecture Series Electrophilic Aromatic Substitution • Electrophilic aromatic substitution: a reaction in which a hydrogen atom of an aromatic ring is replaced by an electrophile H E + + + E + H • In this section: – several common types of electrophiles – how each is generated – the mechanism by which each replaces hydrogen 5 Organic Lecture Series EAS: General Mechanism • A general mechanism slow, rate + determining H Step 1: H + E+ E El e ctro - Resonance-stabilized phile cation intermediate + H fast Step 2: E + H+ E • Key question: What is the electrophile and how is it generated? 6 Organic Lecture Series + + 7 Organic Lecture Series Chlorination Step 1: formation of a chloronium ion Cl Cl + + - - Cl Cl+ Fe Cl Cl Cl Fe Cl Cl Fe Cl4 Cl Cl Chlorine Ferric chloride A molecular complex An ion pair (a Lewis (a Lewis with a positive charge containing a base) acid) on ch lorine ch loronium ion Step 2: attack of
    [Show full text]