Day 1 :
Keynote Forum
Stephen Hanessian
Research Chair, Université de Montreal, Canada
Keynote: A century of natural product synthesis: From concept to practice
Time : 10-45 AM
Biography:
Stephen Hanessian holds the Ionis Pharmaceutical Research Chair at the Université de Montréal. He is also on the faculty in the Departement of Pharmaceutical Sciences, University of California, Irvine as the Director of the Medicinal Chemistry and Pharmacology Graduate Program. His research interests are in organic, bioorganic and medicinal chemistry with nearly 550 original publications and several patents to his credit. His recent book “Design and Strategy in Organic Synthesis” Wiley-VCH, 2013 is a widely acclaimed monograph
Abstract:
The present-day level of achievements in organic synthesis methodology in general, and natural products in particular, is the highest ever compared to as recently as a decade ago. Natural products varying in their structures and biological activities continue to provide synthetic chemists with the incentives to initiate, and the perseverance to pursue challenging research programs. This has also led to the development of innovative methods toward efficient and highly stereocontrolled bond-forming reactions. Stereochemical control in the synthesis of biologically relevant molecules and drug prototypes is a primordial factor in ensuring productive interactions with target enzymes, receptors and other macromolecules. When presented with the structure of a target molecule to synthesize, our first contact is visual. What follows is a subliminal interplay between the eye and the mind's eye, triggering a complex, yet quasi-instantaneous series of visual relational and visual reflexive chemical thought processing events that are a part of the psychobiological basis of generating a synthesis plan. The heuristic aspects of visual and mental thinking paradigms will be discussed in the context of viable synthetic strategies toward biologically relevant molecules.
Keynote Forum
Anny Jutand
Ecole Normale Supérieure, France
Keynote: Contribution of Electrochemistry to Organometallic Catalysis
Time : 10:20-10:55
Biography:
Anny Jutand has studied Chemistry at the University Paris 6 (France). She has obtained her PhD at the University Paris 13 in 1980. After the Post-doctoral study at the Royal Institute of Technology in Stockholm, she moved to the Ecole Normale Supérieure in Paris. She became the Research Director at CNRS in 1992. Her current research interest is transition metal catalysis (Pd, Ru, Cu, Fe, Ni) and focusing on mechanistic investigation by means of electrochemical techniques.
Abstract:
Many organic reactions are catalyzed by transition metals and the catalytic cycle is a succession of chemical steps involving organometallic species whose metal exhibits different oxidation states. Most organometallic complexes may be oxidized or reduced. Consequently, they can be detected and characterized by electrochemical techniques. Moreover, their reactivity in chemical steps can be followed by using the same techniques, taking advantages of the fact that currents are proportional to the concentrations of electroactive species. It is thus, possible to investigate the mechanism of the chemical steps of a catalytic cycle (characterization of the reactive species and their reactivity via the determination of rate constants) so that to determine factors that will control the efficiency of catalytic reactions. This strategy has been used to investigate the role of the base in palladium catalyzed reactions.
- Fundamentals and classification in organic chemistry & Structure, bonding and reactions in organic chemistry
Location: Flemingo 1&2
Chair
Mohammad Hayal Alotaibi
Petrochemical Research Institute, Kingdom of Saudi Arabia
Co-Chair
Chunying Duan
Dalian University of Technology, China
Session Introduction
Yong-Li Zhong
Merck & Co., Inc., USA
Title: A concise and atom-economical suzuki-miyaura coupling reaction using unactivated trialkyl and triarylboranes with aryl halides
Time : 11:15-11:35
Biography:
Yong-Li Zhong completed his Post-doctoral studies in Organic Chemistry from The Scripps Research Institute, during 1998 – 2001. He completed Doctor of Philosophy (PhD) in Organic Chemistry from the Chinese University of Hong Kong, China during 1995 – 1998.
Abstract:
A concise and atom-economical method for the Suzuki-Miyaura coupling of symmetrical trialkyl- and triarylboranes with aryl halides is reported. Key transformations include efficiently utilizing all three alkyl- and aryl- groups of the unactivated trialkyl- and triarylboranes that are commercial available or could be generated in situ from hydroboration of terminal alkenes with borane, and the cross-coupling reaction of the resulting trialkylboranes with aryl halides was run in one-pot fashion. The reported conditions are broadly tolerant of functional groups and heterocycles, making them particularly useful in the context of complex molecule synthesis.
Cheng-Yong Su
Cheng-Yong Su, Sun Yat-sen University, China
Title: Regioselective and enantioselective photoredox catalysis within self-active coordination space of a homochiral Ru(II)-metalloligand-based Pd(II) nanocages
Time : 11:35-11:55
Biography:
Cheng-Yong Su is a Professor of Chemistry at Sun Yat-Sen University. He obtained his PhD from Lanzhou University in the year 1996. He joined Prof. Wolfgang Kaim’s group at Stuttgart University in the year 2001 as an Alexander von Humboldt Research Fellow, and continued his Post-doctoral work with Prof. Hans-Conrad zur Loye at the University of South Carolina in the year 2002. Then he was promoted to a Professor at Sun Yat-Sen University in the year 2004. He is the author of over 200 peer reviewed publications and 6 book chapters. His current research interest is in the field of supramolecular coordination chemistry and materials, focusing on metal–organic materials, catalysis and nanoscience relevant to clean environment and energy.
Abstract:
Regio- and enantioselective photodimerization of naphthols and derivatives is attained within a chiral Ru(II)-metalloligand-based palladium(II) nanocage for the first time. The chiral octahedral Ru(II) catalytic centers on the ΔΔΔΔΔΔΔΔ-/ΛΛΛΛΛΛΛΛ-cage walls convert naphthol derivatives into the exclusive S-/R-napthoquinone products with much higher chiral induction in comparison to the chiral RuL3 catalysts in bulk solution. The enhanced stereoselectivity is rationalized by the interplay of confined-space effect and aryl-aryl interactions between host and guest, which could stereo-control the transition state structures. The reaction mechanism has been investigated by Electron Spin Resonance (ESR) spectra, Cyclic Voltammetry (CV), UV/Vis absorption and fluorescence spectra. The results support the fact that the Ru(II) cage undergoes photoexcitation and subsequent oxidation by O2 to give OH radicals and a Ru(III) intermediate cage. The Ru(III) intermediate is then capable of oxidizing naphthol substrate and removing an electron to provide the arene radical species, which is coupled with OH radical to give the naphthalene-1,2-dione intermediate, followed by rearomatization with the arene radical, and then form a C-C bond to obtain the napthoquinone product without any significant observable byproduct. This dimerization reaction constitutes a very rare example of high asymmetric induction in oxidative biaryl coupling from a chiral photocatalyst, which closely resembles to biological systems.
Mohammad Hayal Alotaibi
Petrochemical Research Institute, Kingdom of Saudi Arabia
Title: Selective dinitration of toluene over zeolites
Time : 11:55-12:15
Biography:
Mohammad Hayal Alotaibi has completed his PhD from School of Chemistry, Cardiff University in the year 2008. His research involves development of novel organic synthetic methods, especially ones that are greener than traditional methods and also, has great interest towards synthesis of compounds with interesting properties. His current research projects involve use of zeolites and solid-supported reagents as catalysts to gain region-selectivity in organic reactions. In addition, he is interested in heterogeneous catalysis especially supported by metal nanoparticles containing gold and palladium. He is a member of many associations including Royal Society of Chemistry (RSC), the American Chemical Society (ACS), American Academy of Forensic Science (AAFS) and the Saudi Chemical Society.
Abstract:
Nitro compounds are very important intermediates for the production of a number of industrial products such as pharmaceuticals, dyes, polymers, and fertilizers. For example, 2,4 dinitrotoluene can be used for the production of Toluene diisocyanate (TDI) and Toluenediamine that can be used to produce Polyurethane, which is widely used in wheels, furniture and has many other applications. We have investigated the dinitration of toluene and nitrotoluenes over zeolite under various reaction conditions with the aim to produce 2,4-DNT region-selectively and with a high yield where various acid anhydrides were used along with various quantities of zeolites and reagents. Nitration of toluene with chloroacetic anhydride over Hï¢ produced 2,4-dinitrotoluene in 98% yield in which 2,4-:2,6-DNT in a ratio of 49:1. Also, propionic anhydride under similar reaction conditions produced 2,4-DNT in 98% with an excellent 2,4-:2,6-DNT ratio of 123:1. This result is simply the highest for direct dinitration of toluene ever recorded, and in contrast to the traditional method, the system containing propionic anhydride, nitric acid, zeolite Hï¢ gave excellent yield of 2,4-dinitroyoluene with excellent selectivity and the only by-product produced during this process was the propionic acid which can be recycled easily. Also, the zeolite can easily be removed from the reaction mixture by a simple filtration, then activated and reused to give good results for several times with or without calcinations. The system was applied successfully to various mono-substituted benzenes (e.g. alkyl and akyloxybenzene). All reactions appeared to be extremely selective for production of 2,4 dinitro isomer or 4-mononitro derivative but highly active anisole and phenetole produced excellent yields for the corresponding 2,4-dinitro derivatives (97% and 96%, respectively).
Hyun-Joon Ha
Hankuk University of Foreign Studies, Korea
Title: New perspective on the synthesis with chiral aziridines
Time : 12:15-12:35
Biography:
Hyun-Joon Ha has obatined his BA from Seoul National University (1982) and PhD from Brown University (1987). He has done his Post-doctoral studies from Stanford University (1987-1988). Then he came back to Korea and worked as a Senior Research Scientist at KIST. In the year 1991, he joined the faculty of the Chemistry department at Hankuk University of Foreign Studies, and is now a Professor of the Chemistry department at the same University. His research includes aziridine chemistry, synthetic methodology, lipase-mediated reactions, asymmetric synthesis with publications of more than 140 papers and 25 patents. He serves as an Associate Editor of Asian J.Org. Chem.
Abstract:
Chiral aziridine-2-carboxylate possesses two important functional groups including carboxylate and aziridine ring which are useful for the synthetic purposes. Since both of (2R)- and (2S)-aziridine-2-carboxylates with phenylethyl group at the ring nitrogen were commercialized in optically pure forms, we have studied to extend their synthetic utilities for the construction of various nitrogen containing molecules in optically pure forms. The C-2 ester group can be transformed to aldehyde, alcohol, amide, ketones, ketoesters and amines bearing diverse substituents with proper stereochemistry in high yields. To carry out the ring-opening or ring-transformation of this aziridine, it should be activated as aziridinium ion or its equivalent with an assistance of proper electrophiles. The regiochemical pathway with substituents at C2 of this non-activated aziridine was disclosed to be dependent on the characteristics of the substituent, electrophile and nucleophile. The aziridine ring opening reaction can be performed with properly functionalized side chain at the aziridine ring by various nucleophiles, which provided an easy access to the diverse nitrogen-containing cyclic and acyclic molecules in asymmetric manner. The highlight of this chemistry was exemplified by an efficient and highly stereoselective synthesis of many biologically important molecules, including sphingosine, D-ribo-(2S,3S,4R)-phytosphingosine, various azasugars, MeBmt, calyculin fragment and tyroscherin.
Chunying Duan
Dalian University of Technology
Title: Merging multifunctional catalytic centers within homochiral metal−organic frameworks: New opportunity for heterogeneous asymmetric catalysis
Time : 12:35-12:55
Biography:
Chunying Duan has completed his PhD in Inorganic Chemistry, Nanjing University, China, and was promoted to a full Professor in 2000. At present he is the Deputy Director of State Key Laboratory of Fine Chemicals, Dalian University of Technology, China. He has dedicated to Chemistry of Werner type architectures, focusing on the biomimetic sensing and molecular imaging, asymmetric catalysis and enzyme-inspired catalysis, and has published more than 200 papers in reputed journals such as Nat. Commun., J. Am. Chem. Soc., Angew. Chem. Int. Ed., and etc.
Abstract:
As the hybrid solids with infinite networks built from organic bridging ligands and inorganic connecting nodes, metal-organic frameworks (MOFs) are ideally suited for catalytic conversions, because they can impose sizeselective restriction through readily fine-tuned channels and pores. Analogues of homogeneous privileged asymmetric metal catalysts or organocatalysts can be synthetically incorporated into MOFs, thus resulting in the incorporation of the selectivity of these single-site catalysts into micropores, and thereby enhancing the shape-, size-, and enantioselectivities of catalytic reactions in comparison to those performed in homogeneous solution. On the other side, the comparable degrees of stereocontrol of delicatedly designed homogeneous asymmetric catalysts could be reached just by incorporation of the much more simplified chiral analogues within MOFs. With the development of synergistic catalysis, combinations of asymmetric catalyst and a second functional auxilliary were employed to realize miscellinous asymmetric transformations, of which the synergy and compatibility of different catalytic cycles still should be carefully tuned to avoid the mutual disturbances among them. Merging asymmetric catalysts and other functional axilliaries within MOFs lead to the spatial discreteness among catalytic centers, avoiding their self-quenchings and mutual disturbances and providing precise knowledge about the pore structure and the nature and distribution of catalytically active sites. Merging polyoxometalates, organic dyes, and noncovalent interaction sites into homochiral MOFs has been realized by us and was proven an powerful tool in construction of MOFs-based heterogeneous synergistic asymmetric catalysts, which provided a new exciting opportunity for the synthesis of enantiopure compounds, including chiral drugs and fine chemicals.
Tuanli Yao
Shaanxi University of Science and Technology, China
Title: Title: Synthesis of 9,10-phenanthrenes via palladium-catalyzed aryne annulation by o-halostyrenes and formal synthesis of (±)-tylophorine
Time : 13:40-14:00
Biography:
Tuanli Yao has completed his PhD from Iowa State University and Post-doctoral studies from University of California, Berkeley. He worked as a Senior Scientist at Deciphera Pharmaceuticals and Associate Researcher at University of Kansas before beginning his career in academics. Currently, he is a Professor at Shaanxi University of Science and Technology. His research interests include aryne chemistry, electrophilic cyclization and palladium catalysis. He has published more than 30 papers in reputed journals.
Abstract:
Phenanthrenes are valuable skeletons found in numerous biologically active natural products and medicinal compounds. They are also a common structural motif in material science because of their unique photochemical and electroluminescent properties. A novel palladium-catalyzed annulation reaction of in situ generated arynes and o-halostyrenes has been developed, which affords moderate to excellent yields of substituted phenanthrenes and tolerate a variety of functional groups such as nitrile, ester, amide, and ketone. This annulation chemistry has been successfully applied to the formal total synthesis of a biologically active alkaloid (±)-tylophorine.
Mei Pan
Sun Yat-sen University, China
Title: Dynamic fl uorescence quenching of pd6(rul3)8 metal-organic cages (mocs) by ferrocene derivatives
Time : 14:00-14:20
Biography:
Mei Pan has received her BS degree in Materials Science from Institute of Crystal Materials, Shandong University, China in the year 2001, and her PhD degree from the Shanghai Institute of Technical Physics of the Chinese Academy of Sciences. She was promoted as a Professor of Chemistry in this year. Her current research interests are centered on photophysics and photochemistry, metal-organic luminescent material, molecular recognition and supramolecular coordination assembly and its application. She has published over 100 articles in international journals, including JACS, Nat. Commun., Chem. Mater. and Chem. Commun.
Abstract:
In supramolecular coordination chemistry field, coordination driven assembly of Metal-Organic Cages (MOCs) with well-defined shapes and unique cavities has drawn great attention in the past decades. A wide variety of applications, such as altering chemical reactivity, intriguing host-guest properties and potentials in chiral recognition, catalysis, as well as drug delivery and release have been thoroughly explored. In the present study, we have reported the host-guest and photochemistry study of ferrocene derivative guests, employing our MOC-16 as a host. The host-guest interaction of three ferrocene (Fc) derivative guests with MOC-16 host were thoroughly studied by NMR spectra, their optical property by UV-Vis, FL spectra and their electrochemical behavior by CV was also studied. Surprisingly, the fluorescence of MOC-16 quenched rapidly when the ferrocene derivative guests were encapsulated by MOC-16 in water. Hence, it was observed that the fluorescence can be recovered simply by extracting guests from the cage cavity with organic solvent.
Ju You Lu
Modern Chemistry Research Institute, China
Title: Copper-catalyzed cross-coupling of 1-haloalkyl-o-carboranes with grignard reagents: An effi cient route to monosubstituted o-carborane derivatives
Time : 14:20-14:40
Biography:
Ju-You Lu has received his BS degree in Chemistry from Hunan University, China, in the year 2008 and PhD in Organic Chemistry from Tsinghua University, China, in the year 2013. He then worked as an Assistant Professor of Organic Chemistry at Xi’an Modern Chemistry Research Institute (MCRI), and joined the research group of Professor Jian Lu. He has been an Associate Professor at State Key Laboratory of Fluorine & Nitrogen Chemicals, MCRI, since 2016. His current research interests include the synthesis of functionalized carborane derivatives. He has contributed more than 20 peer-reviewed publications.
Abstract:
Carboranes, a class of three-dimensional relatives of benzene, having many applications in medicine as boron neutron capture therapy agents, in supramolecular design/materials as building blocks, and in coordination/organometallic chemistry as unique ligands, which have received growing interest. However, their unique structures make derivatization difficult, which results in a limited application scope. Thus, it is important and necessary to develop new methodologies for the functionalization of carboranes. It is obvious that a cross-coupling of 1-haloalkyl-o-carboranes with alkyl and aryl Grignard reagents would be an ideal methodology for the synthesis of cage C-monosubstituted o-carborane compounds. We initially investigated the reaction conditions using 1-(2-bromoethyl)-o-carborane and n-BuMgBr as model substrates. The optimal conditions for the Cu-catalyzed synthesis of mono-substituted o-carboranes are as follows: 20 mol% CuCl2 as the catalyst, 40 mol% PCy3 as the ligand, 2.0 equiv. of Grignard reagents as the coupling partners of 1-haloalkyl-o-carboranes, and the reactions were performed at 25oC under N2. After having optimized the model reaction, we were interested in extending the scope of the coupling reaction, and various o-carborane derivatives were prepared in good to excellent yields by using this copper-based procedure. The present copper-catalyzed protocol can be successfully used for the gram scale synthesis of 1-(n-hexyl)-o-carborane without an apparent decrease in the yield (4.0 g of product, 87.5% yield). The wide substrate scope makes this copper-based strategy remarkably practical for the synthesis of functional boron cluster compounds. We believe this general method will attract much attention and have broad applications in academic and industrial research.
Evgenii S Stoyanov
Novosibirsk Institute of Organic Chemistry, Russia
Title: Chloronium cations, R-Cl+-R, in condenced phases: Formation, thermal stability, and reactivity
Time : 14:40-15:00
Biography:
Evgenii S Stoyanov has received his PhD degree from Vernadsky Institute of Geochemistry and Analytical Chemistry (Academy of Sciences of USSR), Moscow, Russia, and the Doctor of Science degree in Chemistry in 1991 from Mendeleyev University of Chemical Technology, Russia. Presently, he is a Leading Researcher at the Institute of Organic Chemistry (Siberian Branch of Russian Academy of Sciences), Novosibirsk, Russia, and leading the study of carbocations by using the solid super-acids. He has published 139 papers in reputed journals.
Abstract:
Halonium ions (R2Hal+) are reactive intermediates in electrophilic chemistry and are effective methylating and protonating agents for a variety of compounds. Chloronium cations are most reactive and they were obtained as stable carborane salts, (R1-Cl+-R2)(CHB11Cl11ï€) with R1/R2 = CH3, CH2Cl, C2H5 and C3H7, at ambient conditions. We have studied: The thermal stability of the salts of chloronium ions at room and elevated temperature (up to 150ºC), interaction of the R1ï€Cl+ï€R2 cations (R1/R2 = CH3 or CH2Cl) of the solid salts with vapors of CH2Cl2 and CHCl3 and chloronium salts in dichloromethane solutions with accompanying reactions. The asymmetric cations are mostly unstable, for example, the ClСÐ2-Cl+-СÐ3 when kept at room temperature in one day it disproportionated into symmetric cations, (СÐ3)2Cl+ and (СÐ2Cl)2Cl+. At 100oC, disproportionation was completed within 5 minutes. The molecular fragment ClСÐ2ï€(Ð¥) of the compounds with Ð¥ = CHB11Cl11ï€, ï€Cl+ï€Ð¡Ð2Cl, or ï€Cl+ï€Ð¡Ð3, is involved in exchange reactions with CH2Cl2 and CHCl3, converting to CH3-(X) with formation of chloroform and CCl4, respectively. Chloronium cations can also decompose with the removal of the bridging Cl-atom as HCl, to form different carbocations. Hence, they can be a useful in many applications in the conventional chemical practice for special tasks.
Margery Cortes Clerget
University of California at Santa Barbara, USA
Title: Easily recyclable phosphonopeptides as organocatalysts for stereoselective C-C bond creation
Time : 15:00-15:20
Biography:
Margery Cortes-Clerget has completed her PhD in 2015 from the Université Paris 13 (France) under the supervision of Prof. Marc Lecouvey. She is currently doing her Post-doctoral researches in the field of Green Chemistry at the University of California at Santa Barbara under the supervision of Prof. Bruce Lipshutz.
Abstract:
By miming enzymes through H-bonding, hydrophobic effects and in-solvent organization, peptides are great candidates for asymmetric synthesis purpose, acting as multiactivating molecules. Combinatorial screening methods allowed the identification of efficient peptide catalysts for C-X and C-C bonds creation. In 2007, Wennemers introduced the tripeptide H-R-Pro-Pro-Glu-NH2 for Michael addition with great selectivities. Herein we propose an unprecedented combination of aminocatalysis and phosphonic acid activation on a peptide structure. A library of 16 organocatalysts, holding a phosphonic acid was synthesized with a particular emphasis on amino acids modification to install the phosphonic acid on a side chain. These peptides were applied to Michael addition between aldehydes with nitroalkenes with up to 95:5 d.r. and 93:7 e.r at only 1 mol% loading. These catalysts were easily recovered thanks to their aqueous solubility and reused over 10 cycles without any significant loss of selectivity. The impact of the phosphonic acid in place of a carboxylic acid was investigated, as opposite selectivities were observed. Mechanistic investigations were conducted through structural modifications, kinetic studies and modelisation to understand, and, in the future, optimize this library.
- Organometallic chemistry
Location: Flemingo 1&2
Chair
Manoj Kumar
University of Nebraska-Lincoln, USA
Co-Chair
Hyosun Lee
Kyungpook National University, Republic of Korea
Session Introduction
Yong Sheng Bao
Inner Mongolia Normal University, China
Title: Energy-effi cient green catalyst: Supported gold, palladium nanoparticles
Time : 15:20-15:40
Biography:
Yong-Sheng Bao has completed his PhD from NanJing University. He is Associate Professor of College of Chemistry and Environmental Science, Inner Mongolia Normal University. He has published more than 10 papers in reputed journals and has been serving as an editorial board member of repute.
Abstract:
We carried out the research on the supported gold nanoparticles catalyzed aminolysis of ester with inert tertiary amine by C-O and C-N bond activations. Compared with homogeneous catalyst-Pd(OAc)2, the most outstanding feature of supported Au nanoparticles catalyst is their superior ability in catalyzing aminolysis reactions at room temperature. And the catalytic performance of AuNPs didn’t apparently decreased even after recycling five times. On the other hand, we carried out the research on the supported palladium nanoparticles catalyzed ortho-directed CDC reaction of alkylbenzenes and ortho-directed CDC reaction of aldehydes. It is found for the ï¬rst time that metallic state palladium, Pd0, can catalyze the ortho-directed CDC reaction of alkylbenzenes or aldehydes for the synthesis of aromatic ketones via a Pd0/PdII/PdIV catalytic cycle.
Hiroaki Sasai
Osaka University, Japan
Title: Construction of highly functionalized compounds via metal free transformations
Time : 16:00-16:20
Biography:
Hiroaki Sasai received PhD from Keio University and joined Sagami Chemical Research Institute in 1985. He was appointed as an Assistant Professor at Hokkaido University (1988-1992) and as a Lecturer and an Associate Professor at the University of Tokyo (1992-1997). Since 1997, he is a Professor of Osaka University. He has published more than 200 papers in reputed journals and received several awards including the Fluka Prize “Reagent of the Year 1996”, the Chemical Society of Japan Award for Creative Work (2006), Molecular Chirality Award (2011), and Synthetic Organic Chemistry Award, Japan (2016).
Abstract:
Highly efficient [n+2] type annulations have been realized utilizing chiral organocatalysis. Densely functionalized optically active heterocycles having tetrasubstituted carbon stereogenic center were synthesized from allenoate derivatives with either ketimine derivatives or symmetrical dienones. Among the organocatalysts we examined, ï¢-ICD1 showed high enantioselectivity for [2+2] annulation2 and (R)-SITCP3 was effective to [4+2]4 and [3+2]5 annulations.
Manoj Kumar
University of Nebraska, USA
Title: Theoretical modeling of alkanediol decomposition via metal free organocatalysis
Time : 16:20-16:40
Biography:
Manoj Kumar is a Post-doc candidate in Computational Atmospheric Chemistry, University of Nebraska-Lincoln, Lincoln, NE, USA June from 2015 to present. His project title is “Computational Modeling of Atmospheric Chemistry” (with Prof. J S Francisco). He did his Post-doctorate in Computational Organometallic Chemistry, University of Kansas, Lawrence, KS, USA May 2012 to May 2015. His project title is “Molecular Modeling of Olefin Ozonolysis” (with Prof. W H Thompson) and “Molecular Modeling of Rhodium-catalyzed Hydroformylation” (with Prof. T A Jackson). He completed his PhD in Computational Bioinorganic Chemistry, University of Louisville, Louisville, KY, USA during 2007-2012 with thesis title “Computational Modelling of Cobalamin-Dependent Enzymatic Reactions” (with Prof. P M Kozlowski). Summer Research Project, Computational Material Chemistry, Jawahar Lal Nehru Center for Advanced Scientific Research (JNCASR), Bangalore, India, May,2005-July,2005 Thesis title: “Theoretical Analysis of Gold Clusters and Their Interactions with Thiolates” (with Prof. Swapan K Pati). He completed his MSc, Computational Material Chemistry, Panjab University, Chandigarh, India during 2004-06 with the thesis title, “Theoretical Analysis of Finite-Sized Gold Clusters” (with Prof. T K Sau) and BSc, Physics, Chemistry & Mathematics, SVSD PG College, Bhatoli, Himachal Pradesh University, Shimla, India, 2001-04.
Abstract:
Quantum chemical calculations have been carried out to investigate the gas-phase structure, stability and decomposition of the two simplest alkanediols, methanediol and 1,1-ethanediol, in the presence of various catalysts. The calculations reveal that alkanediols may not only exist as monomers, but also as dimers that have high binding energies of 7-11 kcal/mol due to hydrogen bonding among the oxygenate functionalities. Some of these dimers have high dipole moments and thus, may be more easily detected experimentally than the monomers of alkanediols. For the decomposition of alkanediols, the calculations dominantly favor dehydration over dehydrogenation. The relatively low barrier for the decomposition of 1,1-ethanediol suggests that the structure of an alkanediol plays a role in its decomposition. Though the dehydration of alkanediols with or without water catalyst involves large barriers, organic and inorganic acids, and hydroperoxy radical catalytically influence the reaction to such an extent that the dehydration reaction either involve significantly reduced barriers or essentially become barrier less. Considering that alkanediols contain hydroxyl groups and their dimers have high binding energies, the gas-phase dehydration may be self-driven. Since acids are present in significant amounts in the troposphere, results suggest that diol dehydration may be facile under atmospheric conditions.
Suna Balci
Gazi University, Turkey
Title: Catalytic properties and activity of copper and silver containing Al-pillared bentonite for CO oxidation
Time : 16:40-17:00
Biography:
Suna Balci has completed her PhD in the year 1992 from Middle East Technical University, Turkey. She has been working as a Professor in Gazi University. She has published 25 papers in journals indexed by SCI and more than 55 presentations in international conferences.
Abstract:
Al-pillared bentonite (Al-PB) using bentonite obtained from the middle Anatolia region (Hançılı) was synthesized, and Cu@Al-PB and Ag@Al-PB were obtained after the second metal impregnation step. Cu/Al-PB prepared using a hydrothermal method which was obtained with a Cu/(Cu+Al) mole ratio of 0.05 Copper and silver incorporation resulted in approximately 0.35 nm decrease in basal spacing. Surface area of Al-PP measured as 226 m2/g at 5000C was observed to be decreased a little by hydrothermal copper incorporation. XRD, SEM/EDS, scanning electron microscopy/energy dispersive X-ray spectroscopy analyses indicated that impregnation method resulted in a higher copper loading in the structure. Based on XRD, XPS, X-ray photoelectron spectroscopy analysis, the aluminum in all of the samples was in the Al2O3 form with 2s and 2p3 orbitals. Although no copper peaks were observed for Cu/Al-PB, the 2p3 and 2p1 orbitals of copper. It was also observed that the 3d3 and 3d5 orbitals of silver were observed in the copper or silver impregnated samples, respectively. Metal incorporation resulted in especially, an increase in strengths of the bronsted acid peaks in the Fourier transform infrared spectra (FTIR). Intensity of the peaks corresponding to bronsted sites did not change substantially as pyridine desorption temperature increased. Impregnated samples created a decrease in the 50% conversion temperature for CO oxidation. Cu@Al-PB, which was calcined at 5000C, gave a CO conversion that was as high as 100% at approximately 2000C and maintained its activity to 5000C. Hence, in impregnated samples, the reaction may use the surface oxygen which is provided by the metal oxide.
Hyosun Lee
Kyungpook National University, Republic of Korea
Title: Catalytic study of late transition metal complexes in the polymerization of methyl methacrylate
Time : 17:00-17:20
Biography:
Hyosun Lee has completed her PhD from Columbia University, New York in the year 1999 and Post-doctoral studies from the Northwestern University, USA. She came back to Korea and continued her Research at LG Chem., Research Park for 5 years. She joined the faculty of Kyungpook National University, Daegu as an Assistant Professor in 2006 and was promoted to Associate Professor and Professor in 2010 and in 2014, respectively. She is now serving as the Chairman of the Department from 2014 – 2016. Her research interests can be described generally as the design, structure, and synthesis of new coordination complexes and organometallics with interesting properties and mechanistic aspect, and the study of catalysis.
Abstract:
We have prepared and screened cobalt(II), copper(II), zinc(II), palladium(II), and cadmium(II) complexes with several groups of a series of ligands, namely, N,N'-bidentate N-cycloalkyl 2-iminomethylpyridine (group LA), N,N’-bidentate derivatives of N-(pyridin-2-ylmethyl)aniline (group LB), N,N’,N-tridentate N,N-di(2-picolyl)cycloalkylamine (group LC), N,N’,X-tridentate N-substituted 2-iminomethylpyridine and 2-iminomethylquinoline (group LD), N,N'-bidentate N,N-bis[(1H-pyrazol-1-yl)methyl]amines (group LE), and N,N',N-tridentate N’-substituted N,N-bis[(1H-pyrazol-1-yl)methyl]amines (group LF). All these complexes were characterized by spectroscopic methods and X-ray crystallography and applied to catalytic polymerization of Methyl Methacrylate (MMA). Specifically, cobalt(II) and cadmium(II) complexes showed the highest catalytic activity for MMA polymerization in the presence of modified Methylaluminoxane (MMAO) when compared to the corresponding complexes with same ligand system and metal starting materials, such as [CoCl2•6H2O], [CuCl2•2H2O], [ZnCl2], [Pd(MeCN)2Cl2], and [CdBr2•4H2O]. Their activity were in the order of 105 (g PMMA)/(mol cat) h at 60°C and syndiotacticity of poly(methylmethacrylate) (PMMA), characterized by 1H NMR spectroscopy, was Ca 0.73.
Abdol R Hajipour
Isfahan University of Technology, Iran
Title: A versatile catalyst for suzuki and sonogashira reactions of aryl iodides and bromides at room temperature in water as only solvent
Time : 17:20-17:40
Biography:
Abdol R Hajipour is Senior Scientist from University of Wisconsin-Madison, He was Professor in Isfahan University of Technology, His research interest Projects are in field of Nanocatalyst chemistry with team member Shima Bahri.
Abstract:
In this paper, the preparation of an efficient heterogeneous catalyst system based on the immobilization of Pd nanoparticles on a magnetic nanoparticles core (ImmPd-MNPs) is described. The new catalytic system was characterized by TEM, SEM, XRD, EDX, TGA, FT-IR, VSM and ICP analysis. We have demonstrated that ImmPd-MNPs is an efficient and reusable catalyst for the Suzuki–Miyaura and Sonogashira-Hagihara coupling reactions of various types of aryl iodides and bromides in water as a green and environmentally acceptable solvent. Moreover, the reactions were carried out at room temperature efficiently. The catalyst was easily reused by an external magnet from the reaction mixture and recycled six times without significant loss of activity.