Day 2 :
Keynote Forum
Evgenii S Stoyanov
Novosibirsk State University, Russia
Keynote: Carbocations in condensed phases: Stabilization via hyperconjugation, polarization, and hydrogen bonding
Time : 09:30 AM
Biography:
Evgenii S Stoyanov received a PhD degree from Vernadsky Institute of Geochemistry & 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. He has published 139 papers in reputable journals.
Abstract:
A unified concept of the carbocations stabilization in gas, liquid, and solid phases is proposed. For the tert-butyl cation (t-Bu+), which is an iconic example of carbocations, the empirical gas-phase infrared (IR) spectrum shares only a deceptive similarity with the spectrum predicted by theory (for optimized t-Bu+ structure). They have important but so far unnoticed differences. At the same time, the IR spectra of t-Bu+ show a strong similarity to gas and condensed phases, thereby confirming that the nature of intramolecular stabilization of carbocations does not depend on the phase state. The IR spectroscopic analysis of the hydrogen bonding of t-Bu+ with the environment, together with X-ray crystallographic data, reveals that one CH3 group of t-Bu+ differs from the two others. It is presumably polarized and less involved in hyperconjugation in comparison with the other CH3 groups, which are strongly hyperconjugated. The pattern of changes in the IR spectra of carbocations in their salts with the least basic anion (fluorinated carborane CHB11F11ï€) in the series CH3+, C2H5+, i-C3H7+, cyclo-C4H7+, cyclo-C5H9+, methylcyclopentyl+, tert-butyl+, 2-methylbutyl+ and 2,3-dimethylbutyl+, together with the available X-ray crystallographic data, shows that the current understanding of the intramolecular stabilization of carbocations, which is based on the modern ab initio computations contradicts a number of empirical facts. In the report, these contradictions are discussed and an explanation for all the empirical data is offered. Nonetheless, this explanation does not resolve the existing discrepancies with the calculations.
Keynote Forum
Jwo Huei Jou
National Tsing Hua University, Taiwan
Keynote: Blue hazard free candlelight organic light emitting diode
Time : 10:00
Biography:
Jwo-Huei Jou received his PhD in 1986 from University of Michigan, Ann Arbor, Michigan, USA, and worked as a Postdoctoral visiting scientist at IBM-AlmadenrnResearch Center, CA, USA, till 1988 before becoming a faculty in NTHU. He chaired the department from 2006 to 2009. He has published more than 120 journalrnpapers and filed and/or been issued more than 60 patents, and has been serving as an editor of Fluorescent Materials and else.
Abstract:
Candlelight, an Organic Light-Emitting Diode (OLED) will soon become the mainstream lighting due to its numberless disruptive characteristics especially, blue hazard free lighting. This blue hazard free candlelight OLED will disrupt most of the lighting market for being safe, high quality, energy saving, and cost effective. The relatively low color temperature, e.g. 1,900 K, makes it at least 10 times safer in retina protection and 5 times better in melatonin generation as comparing with the 5,000K, bluelight-enriched white CFL, LED, and OLED counterparts. With a joint effort with Wisechip, a passive matrix OLED manufacturer showed the first demo blue hazard free, candlelight OLED street lamp which was installed in Smangus, an arboriginal tribe in Taiwan. These customer affordable luminaries will be made commercially available by the end of 2017. Light Renaissance can hence, be expected with this good light which is friendly to human eyes, physiology, artifacts, ecosystems and environment.
- Biochemistry, Polymer Chemistry, Materials Chemistry | Modern Organic Chemistry and Applications | Physical Organic Chemistry
Location: Flemingo 1&2
Chair
Gregory A Weiss
University of California, USA
Co-Chair
John A Soderquist
University of Puerto Rico, USA
Session Introduction
Jovica Badjic
The Ohio State University, USA
Title: Molecular encapsulation and ractivity with assembled baskets in water
Time : 10:40-11:00
Biography:
Jovica Badjic completed his PhD in 2001 in the area of Organic Chemistry and Post-doctoral studies from UCLA in 2003. He is currently Professor of Chemistry at the Ohio State University. He has published in the area of supramolecular chemistry and catalysis.
Abstract:
The entrapment of guest compounds with artificial hosts allows for controlling local environment and properties of a variety of analytes. In particular, one can use molecular encapsulation for stabilizing reactive intermediates, promoting chemical reactions and modulating conformational dynamics of guests. We recently developed so-called gated molecular baskets for regulating the activation energy (ï„G‡in/out) characterizing the ingress/egress of molecules and thereby chemical reactivity. Interestingly, molecular baskets were additionally found to assemble into stimuli-responsive vesicles in an aqueous environment. These nanostructured materials are capable of trapping nerve agents in water in an allosteric manner. The lecture will focus on presenting our recent efforts toward understanding working mechanisms baskets in controlling the recognition of various guests. I will also discuss the utility of assembled baskets for Cï€H activation of small hydrocarbons in water.
Kohei Torikai
Kyushu University, Japan
Title: 2-Naphthylmethoxymethyl: A Mildly Introducible and Oxidatively Removable Benzyloxymethyl-Type Protecting Group
Time : 11:20-11:40
Biography:
Kohei Torikai has completed his PhD in Osaka University (Prof. Michio Murata) and Post-doctoral studies in Osaka University (Prof. Tohru Oishi) and the University of Tokyo (Prof. Hiroaki Suga). In 2010, he started his academic career at University of Shizuoka as a Research Assistant Professor, and in the same year, moved to Kyushu University as a tenured Assistant Professor. He has published more than 20 papers, received more than 10 awards and grants, and serving as an Editorial Board Member of JSM Chemistry. His research interests are on synthetic organic, natural products, bioorganic, and medicinal chemistry.
Abstract:
Protective groups are still playing important roles in the synthesis of complex molecules, despite the recent negative campaign against using them that increase the E-factor and the number of steps. To expand the variety of protective groups, naphthylmethoxymethyl (NAPOM) was newly developed for the protection of hydroxy (including phenolic hydroxy and carboxy) and mercapto groups. The NAPOM group can be introduced in extremely mild conditions (NAPOMCl, 2,6-lutidine, rt) without concomitant acyl migration in a 1,2-diol system. Furthermore, selective removal of NAPOM in the presence of naphthylmethyl (NAP) and p-methoxybenzyl (PMB), and conversely, that of PMB in the presence of NAPOM, were realized. These results, as well as its easy handling and compatibility with various solvents, show that NAPOM is a novel and useful choice of protective groups.
Gregory A Weiss
University of California, USA
Title: Multi-step enzymatic and organic synthesis with continuous fl ow, thin fi lm fluidics
Time : 11:40-12:00
Biography:
Gregory A Weiss has earned his undergraduate and graduate degrees from the University of California, Berkeley and Harvard, respectively. He was awarded a Ruth Kirschstein National Research Service Award from the NIH, and then he pursued his Post-doctoral studies at Genentech. In the year 2000, he joined the faculty at the University of California, Irvine. He was named a Fellow of the AAAS in 2013; has also been awarded an Ig Nobel Prize in Chemistry for leading the team that unboilied an egg. His laboratory focuses on bioelectronics, single molecule enzymology, membrane proteins, continuous flow protein folding and biocatalysts
Abstract:
Inspired by the multi-step pathways used by organisms to synthesize complex natural products, we have developed thin film microfluidics for iterative chemical transformations generated by a vortex fluidic device; in these micron-scales thin films can drive protein folding and also accelerate catalysis by enzymes. To demonstrate the protein folding capabilities, we rapidly folded recombinant and naturally occurring proteins, including lysozyme from hard-boiled egg whites. Similarly, applying a vortex fluidic device can drive biocatalysis in different soluble enzymes with accelerations up to 15-fold. The thin films avoid clogging, and allow continuous feeding of simple starting materials. Flow chemistry can enable multi-step transformations with compartmentalization of each reaction before the increasingly complex intermediate flows to the next reaction site. Such control is typically not possible using conventional flasks. Assembly line synthesis can allow unprecedented reaction flexibility and processing efficiency. Examples of thin film-based continuous flow synthesis to be presented include both conventional and biosynthesis.
Morgan Stefik
University of South Carolina, USA
Title: Design of novel block co-polymers for solution processing of advanced nanomaterials
Time : 12:00-12:20
Biography:
Morgan Stefik obtained his degree in Materials Engineering from Cal Poly SLO, USA in the year 2005. He has completed his Doctoral studies in Materials Science at Cornell University under the supervision of Prof. U Wiesner and Prof. F J DiSalvo in the year 2010. After two years of Post-doctoral research at Ecole Polytechnique Federale de Lausanne with Prof. M Gratzel, he joined the University of South Carolina in the year 2013 as an Assistant Professor in the Department of Chemistry and Biochemistry. He is the Founding Director of the NSF which supported South Carolina SAXS Collaborative. His research focuses on nano- materials chemistry with emphasis on self-assembly techniques and atomic layer deposition.
Abstract:
The ability to tune nanoscale features in traditional materials can enable new properties or enhanced performance in technologies ranging from optoelectronics to super-capacitors and solar devices. Our lab takes inspiration from the promise of nanomaterials chemistry to advance the capabilities of devices for both energy conversion and storage. One of our core strategies is the design of novel block copolymer self-assembly systems that enable new levels of precision. In this talk, I will focus on recent developments where new amphiphilic block copolymers are synthesized by controlled radical techniques to enable advanced solution processing of inorganic nanostructures. Solution processing is highly scalable, but more subtly is also highly tunable to result in markedly different nanostructures. With one example, we apply thermodynamic concepts to direct the entrapment of block copolymer micelles for self-assembly with precision control. The resulting tunable isomorphic architectures have widespread applications to advance (photo) electrochemical devices.
John A Soderquist
University of Puerto Rico, USA
Title: Asymmetric organoborane conversions via the amazing 9 borabicyclo [3.3.2]decanes
Time : 12:20-12:40
Biography:
John A Soderquist completed his PhD in 1977 from the University of Colorado under the direction of Alfred Hassner. From 1977-79, he was a Post-doctoral scholar under the direction of Nobel Laureate, Herbert C Brown at Purdue University. His independent research career began at the University of San Francisco in 1979, where he became Associate Professor and Department Chairman before moving to the University of Puerto Rico in 1983. Since 1988, he has been a Full Professor of Chemistry, publishing nearly 140 articles, contributing over 400 research presentations to scientific meetings and universities world-wide and directing the thesis studies of nearly 30 PhD students. He has served as a technical consultant for several chemical and pharmaceutical companies.
Abstract:
The stereoselective addition of reagents containing the chiral 10-substituted-9-borabicyclo[3.3.2] decane (BBD) moiety to aldehydes, ketones, aldimines and ketimines will be described. The rigid and robust nature of these systems permits a wide variety of organoborane conversions to not only be conducted in a highly enantioselective manner, but also, it facilitates the recovery of the chiral borane by-product which can be recycled through simple operations. Moreover, numerous chemical conversions can be performed on these organoboranes providing remarkable new reagents for organic synthesis. The origin of the observed selectivities will be presented and discussed in terms of the compact chiral reaction centers provided by the BBD systems.
Shunying Liu
East China Normal University, China
Title: Enantioselective trapping of oxonium ylide with n-benzhydryl-α-imino ester: A rapid access to synthesis of β-tetrasubstituted α-amino acids
Biography:
Shunying Liu has completed her PhD from Wuhan University and Post-doctoral studies from Hong Kong Baptist University and Oxford University. Her research interest is mainly on asymmetric catalysis for multi-component reaction. She has published more than 50 papers in reputed journals.
Abstract:
β-Alkoxy Cβ-tetrasubstituted α-amino acid derivatives are commonly serviceable structural motifs in biologically active natural products and pharmaceuticals. Several efficient methods have been established to construct β-tetrasubstituted α-amino acids. Nevertheless, a rapid access to construction of these complex molecules from simple starting materials under mild conditions are urgently in demand. Multi-component reactions (MCRs) have provided such an approach to realize this goal. Here, a synergistic rhodium(II)/phosphoric acid catalyzed three component reaction of 3-diazooxindoles, alcohols and N-benzhydryl-α-imino ester is successfully developed to provide an efficient strategy for the rapid construction of chiral β-alkoxy Cβ-tetrasubstituted α-amino acid derivatives with high diastereoselectivity (up to 20:1 dr) and excellent enantioselectivity (up to 98:2 er) from simple starting points under mild conditions (Scheme 1). The resulting multi-component products 4 readily afforded 3-spirocyclic oxindole 5 under the standard hydrogenation conditions followed a cyclization with CSCl2 in a good yield remaining excellent enantioselectivity.
Jozef Stec
Marshall B. Ketchum University, USA
Title: Transition metal-assisted total synthesis of natural products
Time : 13:00-13:20
Biography:
Jozef Stec is currently an Associate Professor of Medicinal Chemistry at Marshall B. Ketchum University College of Pharmacy. He obtained MSc (Honors) in Molecular and Pharmaceutical Biotechnology (Gdansk University of Technology); PhD in Organic and Organometallic Chemistry (University of Southampton), and Post-doctoral training in Synthetic Medicinal Chemistry (University of Illinois at Chicago). His research interest is in the area of widely understood synthetic organic and modern medicinal chemistry. His research productivity is documented by manuscripts published in reputed international journals. He is also involved in teaching and numerous professional service activities.
Abstract:
Chemical transformations mediated by transition metals play pivotal role in modern organic chemistry. New reaction development and total synthesis of complex natural products are only a few examples of harnessing the organometallic chemistry. Organozirconium chemistry was successfully utilized in the total synthesis of natural products as exemplified by the recently reported total synthesis of (+)-mucosin. The developed methodology utilized the one-pot two-step zirconocene-mediated co-cyclisation of triene followed by insertion of silylcarbenoid generated in situ, to give the expanded zirconacycle. Protonolysis of zirconacycle followed by the modified Flaming-Tamao oxidation gave the bicyclic alcohol which was oxidized to its corresponding aldehyde by using the Swern protocol. Takaiolefination provided the protected alcohol which was converted to the corresponding carboxylic acid via TBAF deprotection and PDC oxidation. Esterification using diazomethane procedure gave the methyl ester of (+)-mucosin, which is the dextrorotatory enantiomer of the naturally isolated ( )-mucosin methyl ester.
- Advanced trends in organic chemistry | Natural products and heterocyclic chemistry
Location: Flemingo 1&2
Chair
Maria Del Rocio Gamez Montano
Universidad de Guanajuato, Mexico
Co-Chair
Uttam K. Tambar
The University of Texas Southwestern Medical Center at Dallas, USA
Session Introduction
Soon Hyeok Hong
Seoul National University, South Korea
Title: Ruthenium-catalyzed urea synthesis utilizing methanol as the c1 feedstock
Time : 14:05-14:25
Biography:
Soon Hyeok Hong obtained his PhD in 2007 at the California Institute of Technology, under the guidance of Professor Robert H Grubbs. After having Post-doctoral research experience at the University of California, Los Angeles and industrial experiences at Materia, Inc., he began his independent career in academia as an Assistant Professor at Nanyang Technological University with a joint appointment as a National Research Foundation Fellow of the Singapore government in 2008. In 2011, he moved back to his undergraduate school, Seoul National University, where he has been working on organometallic catalysis in developing efficient, practical, and sustainable synthetic methods.
Abstract:
Urea derivatives are commonly found in widespread applications, such as biologically active compounds, pharmaceuticals, agricultural pesticides, dyes for cellulose fibers, and antioxidants in gasoline. Many classical protocols and catalytic transformations have been developed for urea synthesis. Traditional syntheses of urea derivatives use phosgene and isocyanates, which cause tremendous toxicological and environmental problems. Therefore, versatile urea synthesis under mild conditions that avoids environmentally harmful reagents remains a challenge. By applying the concept of acceptorless dehydrogenative coupling, which is a highly advanced environmentally benign strategy for C–O and C–N bond formation directly from alcohols and amines, we developed an unprecedented strategy to synthesize urea derivatives directly from amines utilizing methanol as the C1 source. Symmetrical and unsymmetrical urea derivatives were successfully obtained using methanol as the C1 feedstock. Utilization of methanol as the C1 feedstock could be an ideal solution to reducing the predominant dependence on conventional toxic C1 sources, such as phosgene and isocyanates for urea synthesis.
MarÃa Del RocÃo Gámez Montaño
Universidad de Guanajuato, Mexico
Title: Synthesis of novel tetrazol-chromones via Ugi-azide reaction and in vitro studies for their antibiotic properties
Time : 14:25-14:45
Biography:
Rocío Gámez-Montaño is currently employed at Departamento de Ciencias Naturales y Exactas, Universidad de Guanajuato, Mexico. She was Associate Professor Investigator B during the year 2002-2003 and Associate Professor Investigator C during 2003-2009. She was Chair Professor Investigator A during the year 2009-2015 and Chair Professor Investigator B during the year 2015-present. She completed her Post Doctoral Fellow during (2001-2002) from Institute of Chemistry of Natural Substances, France with Dr. Jieping Zhu. She completed her PhD in Organic Chemistry in the year 2001 from National Autonomous University of Mexico (UNAM).
Abstract:
As a part of our ongoing program to develop short and versatile Ugi-azide based methods toward poly-heterocycles containing the 1,5-disubstituted tetrazole moiety, here I show my resent results about in vitro studies of eighteen newly synthesized tetrazol-chromones against series of pathogenic parasites (Entamoeba histolytica, Giardia lamblia, and Trochomonas vaginalis), pathogenic bacteria (Pseudomonas aeruginosa, and Staphylococcus aureus), and human fungal pathogens (Sporothrixschenckii, Candida albicans, and Candida tropicalis). Moderate to good values were found in all cases, however, the best activity was observed in iodine-containing analogues against G. lamblia and C. albicans. These results have been published recently
Nobuyoshi Morita
Showa Pharmaceutical University, Japan
Title: Gold(I)/(III)-catalyzed synthesis of 2-substituted piperidines; valency-controlled cyclization modes
Time : 14:45-15:05
Biography:
Nobuyoshi Morita has completed his PhD from Osaka University in the year 2003 and then trained as a Post-doctoral fellow at Dortmund University of Technology in Germany (Prof. Norbert Krause). He was then recruited as an Assistant Professor of Organic Chemistry in Showa Pharmaceutical University (SPU) in 2006 and became an Associate Professor of Organic Chemistry in SPU in the year 2016. His researches focus on gold catalyzed reactions
Abstract:
Gold catalysts were initially recognized as ï°-acidic catalysts that activate unsaturated bond (alkynes, allenes and alkenes) for nucleophilic attack to form C-C, C-O, C-N, and C-S bonds. Later, some groups reported the oxophilic character of gold (III) catalysts, which efficiently activated oxygen functinalities even in the presence of an unsaturated bond. We rationalized these observations in terms of the hard and soft acids and bases (HSAB) principle, which states that metal ions in low valence states soft character, whereas metal ions in high positive oxidation states show hard character. Thus, gold(I) catalysts may behave as soft acids and gold (III) catalysts as hard acids. On the basis of this working hypothesis, we developed a synthetic method to obtain two types of cyclic ethers from the same propargylic alcohols by means of valency-controlled gold-catalyzed regiodivergent activation. In order to extend our strategy, we turned our attention to the use of nitrogen nucleophile in place of oxygen nucleophile and explored the synthesis of piperidines from propargylic alcohols bearing nitrogen functionality at the terminal position. Thus, use of hard gold (III) catalyst which resulted in cyclization to furnish piperidines having an acetylenic moiety, due to coordination of hard gold (III) to the oxygen atom at propargylic position. On the other hand, treatment of propargylic alcohols with soft gold (I) catalyst induces Meyer-Schuster rearrangement to afford ï¡,ï¢-unsaturated ketones, which undergo intra-molecular aza-Michael addition to give piperidines bearing carbonyl gorup, due to the activation of the triple bond by coordination of soft gold(I).
Uttam K Tambar
The University of Texas Southwestern Medical Center at Dallas, USA
Title: Allylic functionalization of unactivated hydrocarbons
Time : 15:05-15:25
Biography:
Uttam K Tambar received his AB degree from Harvard University in 2000 and his PhD from the California Institute of Technology in 2006 with Professor Brian Stoltz. After he completed his NIH Post-doctoral Fellowship at Columbia University with Professor James Leighton in 2009, he began his independent research career at UT Southwestern Medical Center in Dallas. He is currently an Associate Professor in the Biochemistry Department, a W W Caruth, Jr. Scholar in Biomedical Research, and a Sloan Research Fellowship. He is interested in asymmetric catalysis, natural product synthesis and medicinal chemistry
Abstract:
We have been exploring the selective functionalization of unactivated hydrocarbons. We have developed a catalytic enantioselective allylic amination of unactivated olefins via a [2,3]-rearrangement (Scheme 1). In this method, a diimido-sulfur reagent serves as the source of nitrogen, and it reacts selectively with terminal olefins through a hetero-ene reaction. The resulting zwitterionic ene adduct undergoes a Pd-catalyzed enantioselective [2,3]-rearrangement to generate chiral amines in high enantiomeric excess. Our approach is conceptually distinct from other enantioselective allylic amination strategies. The synthetic utility of our process is being explored by converting simple and inexpensive terminal olefins into functional materials, such as the pharmaceutical drugs Vigabatrin and Januvia. Based on this chemistry, we have also developed a copper-catalyzed allylic alkylation of unactivated olefins and dienes (Schemes 2 and 3). This represents a general method for functionalizing unactivated hydrocarbons with aromatic, aliphatic, and vinyl Grignard reagents. Our recent discoveries represent a conceptual framework for the generalized functionalization of unactivated olefins.
P K Bhowmik
University of Nevada Las Vegas, USA
Title: Synthesis, optical spectroscopy and laser potential of pyrylium tosylates
Time : 15:25-15:45
Biography:
P K Bhowmik is currently a Professor of Chemistry in the Department of Chemistry and Biochemistry at University of Nevada Las Vegas. He received the 2014 POLY Fellow and 2014 ACS Fellow Awards for his outstanding scientific/professional accomplishments and service to the American Chemical Society. He presently serves on the Editorial Board of 10 technical journals and is an academic Editor for Trends in Green Chemistry, Advances in Research, American Chemical Science Journal and Green and Sustainability Chemistry, and as well as an Advisory Board Member for InnoSense LLC, California, USA.
Abstract:
Pyrylium salts are an important class of organic molecules containing trivalent oxygen atom in six-membered aromatic ring. Versatile methods for the synthesis of a series of four 2,4,6-triaryl-substitued pyrylium tosylate salts with different substituents are reported. The synthesis methods use p-toluenesulfonic acid monohydrate instead of conventional acid catalysts including perchloric acid or boron trifluoride diethyl etherate that pose explosion danger and difficult storage problem, respectively. The chemical structures of these salts were established using Fourier transform infrared, 1H and 13C nuclear magnetic resonance spectroscopic techniques and elemental analysis. Their solubility in different organic solvents was dependent on the substituents in 2nd and 6th positions of phenyl groups. Their thermal stability and thermal property were studied using thermogravimetric analysis and differential scanning calorimeter, respectively. It was observed that, solutions of all four pyrylium tosylate salts absorbed strongly in the blue-near-ultraviolet spectral range and emitted efficiently in the blue-green spectral range depending on the substituent in 2nd and 6th positions of phenyl groups. The fluorescence quantum yield of the salts ranged from 0.56 to 0.33 and under intense ultrashort laser pumping, the solution of the salt, (2,4,6-triphenylpyrylium tosylate), which was having the highest quantum yield demonstrated stimulated emission and laser action with only nominal feedback.
- Poster Session
Location: Atrium
Session Introduction
A Imad A Abu Yousef
American University of Sharjah, United Arab Emirates
Title: nti-fungal activity of novel synthesized chiral schiff bases and their reduction products
Biography:
Imad A Abu-Yousef earned his PhD in Organo-Sulfur Chemistry in 1995 from McGill University (Montreal, Canada). Subsequently, he pursued a Post-doctoral fellowship in Polymer Chemistry at McGill University. His research work was recognized by prestigious institutions that have bestowed awards on him, including the Jordan Higher Education Natural Sciences Award (Jordan, 2010), the National Bank of Sharjah Excellence in Research and Scholarship Award (United Arab Emirates, 2002), and Abdul Hameed Shoman Award for Outstanding Young Chemist Researcher in the Middle East (Jordan, 2000). He has published more than 50 papers in reputed international journals and has been serving as an Editorial Board Member of the Journal of Saudi Chemical Society, an Elsevier Published Journal.
Abstract:
Fungicidal chemicals in crude form have been in use for several decades worldwide. This study aims at evaluating the anti-fungal activity of several novel chiral Schiff bases 3 and their reduction products 4, which were derived from various salicylaldehydes 1 and naturally occurring amino acid L-valine 2, against plant and food pathogens. The anti-fungal activity was assessed in vitro using the Poisoned Food Technique. The studied Schiff base derivatives exerted potent anti-fungal activity even at 25 ppm concentration. Some Schiff base derivatives caused 100% inhibition of Rhizoctonia solani and Colletotrichum capsici, two plant fungal pathogens at 1000 ppm concentration. Even at 100 ppm concentration, many Schiff base derivatives caused potent % inhibition of four common plant fungal pathogens (Rhizoctonia solani, Colletotrichum capsici, Phyllosticta sp., and Curvularia lunata). Indeed, Schiff bases and their reduction products displayed differential anti-fungal activities. The minimum inhibitory concentration (MIC) values of the examined Schiff bases and their reduction products against the respective fungal pathogens were also determined. Our study also reveals that the studied Schiff bases and their reduction products display fungicidal efficacy against common food fungal pathogens including Rhizopus sp., Fusarium sp., Penicillium sp., and Botrytis cinerea at 50-100 ppm concentrations. Collectively, our study demonstrates that the studied Schiff bases and their reduction products possess fungicidal properties against several plant and food fungal pathogens at concentrations as low as 25-50 ppm, suggesting that such compounds can serve as broad-spectrum fungicidal agents for the control of common phytopathogenic fungi.
Makoto Hashimoto
Hokkaido University Graduate School of Agriculture, Japan
Title: Synthesis of photoaffi nity labeling reagents for aromatic -amino acids
Biography:
Makoto Hashimoto has completed his PhD from Graduate School of Phamaceutical Science, Hokkaido University in Japan and Post-doctoral studies from Toyama University in Japan and Bath University. He joined Graduate School of Agriculture, Hokkaido University from 2011.
Abstract:
Photoaffinity labeling is a valuable chemical method for studying the interactions of biologically active molecules with their target molecules. In photoaffinity labeling, a covalent bond is formed between ligand and target proteins upon irradiation with UV light. For instance, to study biologically active peptide interactions for a target protein, a photoreactive aromatic ï¡-amino acid will be powerful probe for photoaffinity labeling. Photoreactive phenylalanine derivatives has been used for this purpose, but the construction of these compounds are base on condensation of photophore and ï¡-amino acid equivalents. Especially, trifluoromethylphenyl diazirine and benzophenone, which are very common photophores for photoaffinity labeling, are also of same status. We encouraged direct constructions of photophores on optically pure ï¡-amino acids as photoreactive phenylalanine derivatives. Tryptophan sometimes plays important role for biological activities. But the high reactivities of indole skelton on tryptophan hampered to synthesis of photoreactive tryptophan derivetives for photoaffinity labeling. Careful reaction setting to constructions of trifluoromethyldiazirine on indole promoted us to synthesize tryptophane metabolites comprehensively.
Biography:
Hamad Al-Matar is Assistant Professor in Organic Chemistry at Kuwait University, Kuwait. In the year 2001, he completed PhD in Organic Chemistry from University of Sussex, Brighton, UK. In the year 1997, he completed his MSc in Organic Chemistry from Howard University, Washington DC, USA.
Abstract:
The reaction of active methylenes (cyclic and acyclic), phenols, 2-thiazolylacetonitrile and alkyl pyridazinyl carbonitriles with benzylidine malononitrile in ethanolic chitosan afforded amino pyrancarbonitriles 2, benzopyrancarbonitriles 3, thiazolopyridine 4, and benzopyridazines 5 respectively, in yields comparable to those obtained in ethanolic piperidine [1-3]. Much lower yields were obtained in aqueous solutions.
Biography:
Xu Jing has completed his PhD from Dalian University of Technology. He is an associate professor in college of chemistry and environmental science of Hebei University.
Abstract:
Metal-organic frameworks (MOFs) and Metal-organic polyhedra systems that constructed through the coordination of metal ions and organic linkers, represent a unique class of functional molecular containers that display interesting recognition properties and fascinating reactivity reminiscent of the natural enzymes. These architectures generating welldefined cavities provided specific inner environments for selective bonding of guest molecules and catalyzing their reactions. The great flexibility in terms of the molecular design and the potential benefits of integrating inorganic and organic components within a single composite make them interesting candidates for supramolecular catalytic chemical transformation. Yet only few "artificial enzymes" achieved the magnificent catalysis of natural enzymes. Most metal-organic cages don't constitute specific interactions capable of encapsulating guest molecules and catalyzing the reactions, due to the intrinsic difficulties on the producing guest-accessible sites inside the well-define spaces. Through incorporating amide-containing multidentate chelators within the ligand backbone, herein we reported the synthesis and catalytic properties of several metal- organic hosts to investigate the possibility in the application of molecular sensing and molecular flasks for enzymatic catalysis.
Ali Morsali
Tarbiat Modares University, Iran
Title: Pore size and interactions effect on removal of dyes with metal-organic frameworks
Biography:
Ali Morsali completed his High School Diploma in the year 1991 in Experimental Sciences, from Hakim Hidaji High School, Hidaj, Zanjan, Iran. He completed BSc (during 1992-1995), in Pure Chemistry from Tarbiat Moallem University, Tehran, Iran and MSc in Inorganic Chemistry (during 1996-1998) from Zanjan University, Zanjan, Iran. He obtained his PhD in Inorganic Chemistry (during 1999-2003) from Tarbiat Modares University (TMU), Tehran, Iran.
Abstract:
Two typical highly porous metal-organic framework (MOF) materials based on lead(II), [Pb(4-bpdh)(NO3)2(H2O)]n (TMU-1) and [Pb(4-bpdh)(NO3)2]n (TMU-2) have been used for the removal of harmful dyes (anionic dye methyl orange (MO) and cationic dye methylene blue (MB)) from contaminated water via adsorption. The adsorption capacities of TMU- 1 and TMU-2 are much higher than those of an activated carbon. Our results show that the difference between MO and MB adsorption in TMU-1 and TMU-2 could be related to pore size and coordinated H2O interactions. Dye elimination has also been studied by the use of adsorption/desorption process. The delivery of dyes from compounds in methanol at room temperature was determined by UV/Vis spectroscopy.
Courage Akpan
Eastern Mediterranean University, Turkey
Title: A New perylene diimide dye with powerful binding sites for metal ions
Biography:
Courage Akpan holds a Bachelor’s degree in Biochemistry at Ambrose Alli University in Nigeria. Also, he has been a graduate member of the Nigerian Institute of Management and currently rounding up his Master’s degree in Organic Chemistry at Eastern Mediterranean University in North Cyprus. In his Master’s studies, he has studied the synthesis of dye molecules and their applications. Therefore, he has specialized in synthetic organic dye chemistry. He is enthusiastic, exceptionally well-organized, and he looks forward to pursuing his academic career in Organic Chemistry.
Abstract:
Metal binding is expected to make changes in photophysical and photochemical properties of sensitizers such as wavelength shifts and intensity changes in absorption and emission spectra. Perylenechromophoric dyes are excellent materials of aromatic π-conjugated heterocyclic family. The rigid structure of perylenechromophores causes strong intermolecular π-π interactions giving rise to versatile optical and electronic characteristics. With the advantages of tailoring the imide and bay-positions of perylene structures, exclusive benefits were achieved such as n-type semiconducting character, extended absorption coefficients, high photoluminescence quantum yields, self-assembly behaviours, thermal and photostabilities. A new perylenediimide dye containing powerful binding site for metal ions was synthesized successfully. The synthetic product was characterized by FTIR, NMR, UV-vis, Emission, TGA, DSC, and cyclic and squarewave voltammetry techniques. In addition, the photophysical and electrochemical properties were investigated in detail. The high thermal and photostabilities, including important photonic properties, make the new dye a potential candidate for various photo-sensing applications.
Joanna Feder Kubis
Wrocław University of Technology, Poland
Title: Design and synthesis of new chiral ionic liquids as potential antielectrostatic agents
Biography:
She is Research Associate from the year 2009 till present at Wroclaw University of Technology, Faculty of Chemistry at Wrocław Area, Poland Her specialization in organic chemistry and technology, chemistry of natural products (Open)2 honors and awards in The development of educational and scientific potential of the young academic staff of Wroclaw University of TechnologyThe development of educational and scientific potential of the young academic staff of Wroclaw University of Technology She was Research Associate at Poznan University of Technology from September 2001 – till May 2008 at Poznań Area, Poland.
Abstract:
Academic research on ionic liquids, across many varied applications, is strong and still growing area of interest. New chiral imidazolium-based ionic liquids containing (1R,2S,5R)-(–)-menthol substituent, having symmetrical structure of the salts, have been synthesized and characterized. Monocyclic terpen alcohol: (1R,2S,5R)-(–)-menthol, obtained from a variety of mint (Menthae L.), was used as a substrate in two different reactions to obtain 1,3-bis[(1R,2S,5R)-(–)-menthoxymethyl]imidazolium chloride [1], which is a prototype of chiral ionic liquids. After that, metathesis of this symmetrical imidazolium chloride with various organic and inorganic salts in menthol or water/menthol solution was carried out. The ion exchange reaction goes smoothly, with the satisfactory exceed (from 94 to 99%). Discussed symmetrical salts belong to Chiral Ionic Liquids (CILs) where the chirality resides in the cation and is associated with the presence of optical active (1R,2S,5R)-(–)-menthol. Obtained symmetrical salts are hydrophobic, and air- and moisture-stable under ambient conditions. Moreover, they are non-volatile and non-flammable. Some of the 1,3-bis[(1R,2S,5R)-(–)-menthoxymethyl]imidazolium salts [i.e.: chloride, bis(trifluoromethanesulfonyl) imide, acesulfame, saccharinate] possess excellent antielectrostatic properties and their ability to drain the surface charge is similar to these of a known antistatic agent (Catanac 609: American Cyanamin Co.).
Marina Galdino da Rocha Pitta
Federal University of Pernambuco, Brazil
Title: Synthesis and in vitro anticancer activity of two thiazacridine derivatives
Biography:
Marina Galdino da Rocha Pitta has completed her Doctorate degree and is currently, pursuing her Post-doctoral from Federal University of Pernambuco. During her Post-doctorate, she was an exchange student at Haute école d'ingénierie et d'architecture Fribourg, HES SO, Switzerland and completed a specialization in Pharmaceutical Engineering at Well E&C, South Korea. She has published more than 12 papers in reputed journals.
Abstract:
Cancer is considered as one of the most challenging diseases to treat because despite advancements in our understanding of the disease, several types still have no cure and some tumour cells have become resistant to the drugs currently available in clinics. Acridine and their derivatives represent a very interesting class of molecules due to their broad spectrum of activity, being used as chemotherapeutic agents against bacteria, protozoa, malaria, HIV and cancer. The present work describes the synthesis and the cell antiproliferation activity of compounds 3-Acridin-9-ylmethyl-5-acridin-9-ylmethylene-thiazolidine- 2,4-dione (LPSF - AA2) and 3-Acridin-9-ylmethyl-5-(4-methyl-benzylidene)-thiazolidine-2,4-dione (LPSF - AA4) which are derived from acridine-thiazolidinediones nucleus. The two synthetized thiazacridines were synthetized through three reaction steps: n-alkylation, Knoevenagel condensation followed by a Michael addition reaction. The structures of all the compounds were established by their spectroscopic and spectrometric data such as 1H NMR, IR and LC-MS. The compounds LPSF - AA2 and LPSF - AA4 were evaluated in vitro as potent anticancer agents in Raji, Jukart, T47D and NG97 cancer cell lines. These cells were subjected to anti-proliferative and apoptosis assays to elucidate the mechanism of cytotoxicity. The compound LPSF - AA2 showed high cytotoxicity (IC50 7.64±3.50 μM) on Burkitt´s lymphoma cells whereas LPSF - AA4 exhibited antiproliferative activity against the acute T cell leukemia with IC50 value of 30.14±0.65 μM. It was also observed that both thiazacridine derivatives were non-toxic against non-tumor cells compared to amsacrine drug. Interestingly, LPSF - AA2 didn’t induced apoptosis of Raji cells but led them to cell cycle arrest
Ya Jun Hou
Sun Yat-sen University, China
Title: Self-assembly, host-guest chemistry and visble-light induced dmso degradation of pd6(fel3)8 metalorganic cages
Biography:
Ya-Jun Hou has received her BS in Applied Chemistry from Sun Yat-sen University, China in the year 2014, and is currently pursuing her PhD in Physical Chemistry from Sun Yat-Sen University. Her research interests are supramolecular coordination assembly and its application.
Abstract:
Recently, our group has reported an octahedral Pd(II)-Ru(II) heteronuclear Metal-Organic Cage (MOC) compound whose host-guest chemistry and chirality has been thoroughly studied. In this work, we introduced Fe(II) to the construction instead of Ru(II) and thus obtained a MOC with same structure proved by X-ray single crystal diffraction through stepwise self-assembly of diimine ligand, naked Fe(II) and Pd(II) in mild conditions. The assembly process, affinity with phenylacetylene derivatives, electrochemistry as well as photochemistry properties were carefully investigated by NMR technique, CV test, UVVis and FL spectra, respectively. It was observed that, the Pd(II)-Fe(II) MOC showed good performance for degradation of DMSO to CH4 using TEOA as sacrificial agent under visible-light irradiation, with TON up to 285 in 6 h.
Kai Wu
Sun Yat-sen University, China
Title: Dynamic fluorescence quenching of Pd6(RuL3)8 Metal-Organic Cages (MOCs) by ferrocene derivatives
Biography:
Kai Wu has received his BS in Chemistry from Lanzhou University, China in the year 2013. Currently, he is pursuing his PhD degree from Sun Yat-Sen University. His current research interests are centered on supramolecular coordination assembly and its application.
Abstract:
In supramolecular coordination chemistry field, coordination driven assembly of Metal-Organic Cages (MOCs) with welldefined 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.
- 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.