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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.
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    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.
  • Reactions of Benzene & Its Derivatives

    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