Open Access. Powered by Scholars. Published by Universities.®
Physical Sciences and Mathematics Commons™
Open Access. Powered by Scholars. Published by Universities.®
- Discipline
- Institution
-
- University of Windsor (5)
- City University of New York (CUNY) (1)
- Dartmouth College (1)
- Georgia Southern University (1)
- Louisiana State University (1)
-
- Murray State University (1)
- SelectedWorks (1)
- Trinity University (1)
- University at Albany, State University of New York (1)
- University of Arkansas, Fayetteville (1)
- University of Louisville (1)
- University of Nebraska - Lincoln (1)
- University of New Haven (1)
- West Virginia University (1)
- Western University (1)
- Publication
-
- Chemistry and Biochemistry Publications (5)
- Chemistry Faculty Research (1)
- Chemistry Publications (1)
- Chemistry and Chemical Engineering Faculty Publications (1)
- Dartmouth Scholarship (1)
-
- Electronic Theses and Dissertations (1)
- Graduate Theses and Dissertations (1)
- Graduate Theses, Dissertations, and Problem Reports (1)
- Honors College Theses (1)
- LSU Doctoral Dissertations (1)
- Legacy Theses & Dissertations (2009 - 2024) (1)
- Murray State Theses and Dissertations (1)
- Patrick Dussault Publications (1)
- Publications and Research (1)
- Sergey N. Gorodsky (1)
- Publication Type
Articles 1 - 19 of 19
Full-Text Articles in Physical Sciences and Mathematics
Enabling Technologies For Chemical Synthesis: I. Selective Microwave Heating; Ii. Synthesis And Regioselective Cyclotrimerizations Of Tethered 1,6-Diynes, Amir Tavakoli
Graduate Theses, Dissertations, and Problem Reports
Reaction discoveries, method developments, and technology advancements lie at the heart of synthetic organic chemistry. These innovations are essential for creating and manipulating complex molecules, which are the building blocks of many important chemical compounds, including pharmaceuticals, materials, and agrochemicals. Here, we first describe new methods to prepare neopentylene-tethered (NPT) 1,6-diynes which are valuable substrates for reaction discovery and target-oriented synthesis, especially in benzannulation strategies toward illudalane natural products. NPT 1,6-diynes have been employed as coupling partners in cyclotrimerization reactions for the synthesis of highly substituted benzene rings which present a persistent challenge in chemical synthesis and are underrepresented scaffolds …
New Synthetic Reactions Enabled By Protected Oxyallyl And Amidoallyl Cations, Binod Nepal
New Synthetic Reactions Enabled By Protected Oxyallyl And Amidoallyl Cations, Binod Nepal
LSU Doctoral Dissertations
This dissertation entails design and development of two new synthetic methodologies made possible through the generation of cationic species, namely oxyallyl and amidoallyl cations. Chapter 1 involves literature survey on generation and trapping of oxyallyl cations. Mostly known for cycloaddition reactions with these elusive species, the most recent approach of direct nucleophilic capture of oxyallyl cations are discussed. Apt design of substrates and reaction conditions by Kartika Group to access a-electrophilic carbon towards the synthesis of a variety of value-added compounds, i.e., 1,4- and 1,6-dicarbonyls, carbazoles, densely substituted pyrroles and furans are elaborated.
Chapter 2 focuses on our discovery of …
Synthesis And Evaluations Of “1,4-Triazolyl Combretacoumarins” And Desmethoxy Analogs, Tashrique A. Khandaker, Jessica D. Hess, Renato Aguilera, Graciela Andrei, Robert Snoeck, Dominique Schols, Padmanava Pradhan, Mahesh K. Lakshman
Synthesis And Evaluations Of “1,4-Triazolyl Combretacoumarins” And Desmethoxy Analogs, Tashrique A. Khandaker, Jessica D. Hess, Renato Aguilera, Graciela Andrei, Robert Snoeck, Dominique Schols, Padmanava Pradhan, Mahesh K. Lakshman
Publications and Research
1,4-Triazolyl combretacoumarins have been prepared by linking the trimethoxyarene unit of combretastatin A4 with coumarins, via a 1,2,3-triazole. For this, 4-azidocoumarins were accessed by a sequential two-step, one-pot reaction of 4-hydroxycoumarins with (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), followed by reaction with NaN3. In the reaction with BOP, a coumarin-derived phosphonium ion intermediate seems to form, leading to an O4-(benzotriazolyl)coumarin derivative. For the CuAAC reaction of azidocoumarins with 5-ethynyl-1,2,3-trimethoxybenzene, catalytic [(MeCN)4Cu]PF6 in CH2Cl2/MeOH with 2,6-lutidine, at 50 oC, was suitable. The 4-azidocoumarins were less reactive as compared to PhN3 and …
On The Limited Role Of Electronic Support Effects In Selective Alkyne Hydrogenation: A Kinetic Study Of Au/MoX Catalysts Prepared From Oleylamine-Capped Colloidal Nanoparticles, James E. Bruno, K. B. Sravan Kumar, Nicolas S. Dwarica, Alexander Hüther, Zhifeng Chen, Clemente S. Guzman Iv, Emily R. Hand, William C. Moore, Robert M. Rioux, Lars C. Grabow, Bert D. Chandler
On The Limited Role Of Electronic Support Effects In Selective Alkyne Hydrogenation: A Kinetic Study Of Au/MoX Catalysts Prepared From Oleylamine-Capped Colloidal Nanoparticles, James E. Bruno, K. B. Sravan Kumar, Nicolas S. Dwarica, Alexander Hüther, Zhifeng Chen, Clemente S. Guzman Iv, Emily R. Hand, William C. Moore, Robert M. Rioux, Lars C. Grabow, Bert D. Chandler
Chemistry Faculty Research
We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylaminecapped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ~2.5 nm in diameter. The catalysts showed high alkene selectivity (>90%) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25– 40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate …
Nucleophilic Phosphine Addition: Exploration Of Novel Alkyne Transformations, Brett Pierce
Nucleophilic Phosphine Addition: Exploration Of Novel Alkyne Transformations, Brett Pierce
Murray State Theses and Dissertations
Nucleophilic phosphine catalysis has demonstrated its value in synthetic chemistry by allowing for mild carbon-carbon bond formation. Many phosphine-catalyzed reactions with electron-deficient alkynes have been reported in recent years, leading to an array of valuable products. Stemming from this field of study, phosphines can also be utilized as mild chemoselective reductants for alkynes, resulting in the corresponding alkenes. Herein, a mild, stereoselective, phosphine-mediated partial reduction of alkynes to (E)- and (Z)-alkenes is described. Specifically, a general method for the partial reduction of ynoates to the corresponding (E)- and (Z)-enoate, …
Anchoring Cu 1 Species Over Nanodiamond-Graphene For Semi-Hydrogenation Of Acetylene, Fei Huang, Yuchen Deng, Yunlei Chen, Xiangbin Cai, Mi Peng, Zhimin Jia, Jinglin Xie, Dequan Xiao, Xiaodong Wen, Ning Wang, Zheng Jiang, Hongyang Liu, Ding Ma
Anchoring Cu 1 Species Over Nanodiamond-Graphene For Semi-Hydrogenation Of Acetylene, Fei Huang, Yuchen Deng, Yunlei Chen, Xiangbin Cai, Mi Peng, Zhimin Jia, Jinglin Xie, Dequan Xiao, Xiaodong Wen, Ning Wang, Zheng Jiang, Hongyang Liu, Ding Ma
Chemistry and Chemical Engineering Faculty Publications
The design of cheap, non-toxic, and earth-abundant transition metal catalysts for selective hydrogenation of alkynes remains a challenge in both industry and academia. Here, we report a new atomically dispersed copper (Cu) catalyst supported on a defective nanodiamondgraphene (ND@G), which exhibits excellent catalytic performance for the selective conversion of acetylene to ethylene, i.e., with high conversion (95%), high selectivity (98%), and good stability (for more than 60 h). The unique structural feature of the Cu atoms anchored over graphene through Cu-C bonds ensures the effective activation of acetylene and easy desorption of ethylene, which is the key for the outstanding …
Nicholas Reactions Of Alkynyl- And Alkenyltrifluoroborates, Brent St. Onge, James R. Green
Nicholas Reactions Of Alkynyl- And Alkenyltrifluoroborates, Brent St. Onge, James R. Green
Chemistry and Biochemistry Publications
The Lewis acid mediated Nicholas reaction of potassium alkynyltrifluoroborates and propargyl acetate- hexacarbonyldicobalt complexes affords 1,4-diyne dicobalt hexacarbonyl complexes in good yields. The analogous Nicholas reactions of potassium alkenyltrifluoroborates give 1,3-enyne dicobalt hexacarbonyl complexes in most cases, although the initial site of reaction can vary. Potassium vinyltrifluoroborate itself affords alkynylcyclopropane complexes.
The Preparation And Characterization Of Tetrafluoro-Lambda~6~-Sulfanes, Linbin Zhong
The Preparation And Characterization Of Tetrafluoro-Lambda~6~-Sulfanes, Linbin Zhong
Legacy Theses & Dissertations (2009 - 2024)
Synthetic access to systematically substituted tetrafluoro-λ6-sulfanes was challenging and the research in this area had been largely abandoned. The original reports of disubstituted-tetrafluoro-λ6-sulfanes were limited to substitution by diphenyl and dialkyl groups. The dialkyl-tetrafluoro-λ6-sulfanes were reactive while the diphenyl substituted compounds showed decreased reactivity. In this dissertation, the systematic substitution on tetrafluoro-λ6-sulfanes has enabled the studies of the substitution effects on reactivity.
Iodine-Initiated Hydration Of Internal Alkynes, Nicholas J. Shuber, Karelle Aiken
Iodine-Initiated Hydration Of Internal Alkynes, Nicholas J. Shuber, Karelle Aiken
Honors College Theses
The iodine-initiated hydration of internal alkynes is a novel, green, and inexpensive synthetic pathway in comparison with the commonly used transition metal catalyzed reactions. This can be a useful alternative in many fields, academic or industrial. This experimental design has been used successfully on terminal alkynes and is now being extended to internal alkynes. Through systematic probing of the reaction conditions, we have gleaned sufficient information to determine a strong mechanistic hypothesis based on neighboring group participation. Here in, we will report our result with a series of internal, keto alkynes reacted under ambient conditions with iodine in “wet” solvent. …
[3+2] Annulation Of Cyclopropylanilines With Alkynes Under Photocatalysis, Theresa Ha Nguyen
[3+2] Annulation Of Cyclopropylanilines With Alkynes Under Photocatalysis, Theresa Ha Nguyen
Graduate Theses and Dissertations
Over the past decade, pharmaceutical industries have prioritized their focus on discovering new innovative drugs, yet the syntheses are often either inefficient or the approach of environmental sustainability presents a great deal of concern. Moreover, the methodology developments for amine syntheses have continued to flourish due to their important role and wide use in pharmaceutics. Yet their syntheses often lack sustainability and efficiency. Synthetic chemists have continued to explore potential innovative avenues for conducting chemical reactions more effectively and efficiently. One of the most abundant, renewable natural resources is solar energy and to harvest, use, and store it directly is …
Synthesis Of Tenuifolin Via Intramolecular Nicholas Reaction, Sinisa Djurdjevic, James R. Green
Synthesis Of Tenuifolin Via Intramolecular Nicholas Reaction, Sinisa Djurdjevic, James R. Green
Chemistry and Biochemistry Publications
The synthesis of the Cinnamomum homosesquiterpenoid tenuifolin has been accomplished by way of an intramolecular Nicholas reaction of the [Co2(CO)6] complex of an alkyne-substituted biaryl for construction of the seven-membered ring. The cyclization features the reaction of a nonactivated arene ring with the propargyldicobalt cation to give the dibenzocycloheptyne-Co2(CO)6.
Regioselective Synthesis Of Tetraalkynylarenes By Consecutive Dual Sonogashira Coupling Reactions Of The Bis(Triflate) Of 4,5-Diiodobenzene-1,2-Diol, Thomas J. Fisher, Patrick H. Dussault
Regioselective Synthesis Of Tetraalkynylarenes By Consecutive Dual Sonogashira Coupling Reactions Of The Bis(Triflate) Of 4,5-Diiodobenzene-1,2-Diol, Thomas J. Fisher, Patrick H. Dussault
Patrick Dussault Publications
Abstract The regioselective synthesis of nonsymmetric tetraalkynylarenes has been readily achieved through consecutive sets of Sonagashira cross-coupling reactions of the bis(triflate) derivative of 4,5-diiodobenzene-1,2-diol. The initial coupling reactions proceeded with nearly complete selectivity for the reaction at the Ar–I linkages. Subsequent coupling reactions at the Ar–OTf linkages were efficiently conducted. The tetraalkynylarene products are of interest as components of organic molecular materials.
Exploration Of The Chemistry Of Alkynes And Selectfluor : Search For Cytotoxic Agents From The Amazonian Rainforest., Zhuang Jin
Electronic Theses and Dissertations
Vicinal dithioethers and alkenyl thioethers were synthesized under environmentally friendly conditions using alkyne and thiol in water. Alkynes were also used to develop a multibond-fonning reaction that fonned cyclic ketones or ketoesters through a goldcatalyzed intramolecular oxygen transfer isomerization of 2-alkynyl-l ,5-diketones or 2- alkyny 1-5 -ketoesters. The investigation of Selectfluor chemistry yielded a highly stereoselective synthesis of fluoroalky (E)-a,ß-unsaturated ketones from allenyl esters, through a gold-catalyzed rearrangement that produced an intennediate dienyl ester. When Selectfluor was combined with copper, it produced two oxidative systems, F-TEDA-BF4 and F-TEDAPF 6, both of which efficiently converted amides into imides at room temperature …
Concentration Oscillations In The Processes Of Unsaturated Compounds Oxidative Carbonylation. 1. Processes Of Acetylene And Phenylacetylene Oxidative Carbonylation (In Russian), Sergey N. Gorodsky, Katarina Novakovic
Concentration Oscillations In The Processes Of Unsaturated Compounds Oxidative Carbonylation. 1. Processes Of Acetylene And Phenylacetylene Oxidative Carbonylation (In Russian), Sergey N. Gorodsky, Katarina Novakovic
Sergey N. Gorodsky
This review describes the processes of oxidative carbonylation of acetylene and phenylacetylene, occurring in the oscillatory mode under conditions of homogeneous catalysis by palladium complexes.
Synthesis Of ‘Spacer’-Naproxen [2-(6-Methoxybiphenylen-2-Yl)Propanoic Acid] And -Isonaproxen [2-(7-Methoxybiphenylen-2-Yl)Propanoic Acid], Juan A. González Gómez, James R. Green, Peter C. Vollhardt
Synthesis Of ‘Spacer’-Naproxen [2-(6-Methoxybiphenylen-2-Yl)Propanoic Acid] And -Isonaproxen [2-(7-Methoxybiphenylen-2-Yl)Propanoic Acid], Juan A. González Gómez, James R. Green, Peter C. Vollhardt
Chemistry and Biochemistry Publications
The CpCo(CO)2-catalyzed cocyclization of 1,2-diethynyl- 4-methoxybenzene with alkynes can be applied to the synthesis of ‘spacer’-naproxen [2-(6-methoxybiphenylen-2-yl)propanoic acid] and its 7-methoxy isomer, ‘spacer’-isonaproxen. While unsymmetrical alkynes are incorporated without regioselectivity, the methoxy group in 6-methoxy-2,3-bis(trimethylsilyl)biphenylene directs electrophiles to C-3, thus allowing for regiochemical differentiation between the 2- and 3-positions.
Bf3·Oet2 Catalyzed Reaction Of Donor-Acceptor Cyclobutanes With Terminal Alkynes: Single Step Access To 2,3-Dihydrooxepines, Ben P Machin, Brian L Pagenkopf
Bf3·Oet2 Catalyzed Reaction Of Donor-Acceptor Cyclobutanes With Terminal Alkynes: Single Step Access To 2,3-Dihydrooxepines, Ben P Machin, Brian L Pagenkopf
Chemistry Publications
In the presence of BF3˙OEt2 cyclobutane-1,1-diesters undergo a reaction with terminal alkynes to quickly access dihydrooxepines.
Benzocycloheptynedicobalt Complexes By Intramolecular Nicholas Reactions, Y. Ding, James R. Green
Benzocycloheptynedicobalt Complexes By Intramolecular Nicholas Reactions, Y. Ding, James R. Green
Chemistry and Biochemistry Publications
Lewis acid mediated intramolecular Nicholas reactions of aryl (Z)-enyne propargyl acetate-CO2(CO)(6) complexes 1 afford benzocycloheptenyne-CO2(CO)(6) complexes 2 and their heterocyclic analogues.
Intramolecular Pauson-Khand Reactions Of Cycloheptynedicobalt Complexes, Ahmed B. Mohamed, James R. Green, Jason Masuda
Intramolecular Pauson-Khand Reactions Of Cycloheptynedicobalt Complexes, Ahmed B. Mohamed, James R. Green, Jason Masuda
Chemistry and Biochemistry Publications
Cycloheptyne-Co-2(CO)(6) complexes bearing alkenes tethered by oxygen, sulfur, and nitrogen atoms undergo Pauson-Khand reactions to afford tricyclic compounds containing a fused 7,5-ring system.
Synthetic Studies In Phytochrome Chemistry, Peter A. Jacobi, Imad Odeh, Subhas Buddhu, Guolin Cai, Sundaramoorthi Rajeswari, Douglas Fry, Wanjun Zheng, Robert W. Desimone, Jiasheng Guo, Lisa D. Coutts, Sheila I. Hauck, Sam H. Leung, Indranath Ghosh, Douglas Pippin
Synthetic Studies In Phytochrome Chemistry, Peter A. Jacobi, Imad Odeh, Subhas Buddhu, Guolin Cai, Sundaramoorthi Rajeswari, Douglas Fry, Wanjun Zheng, Robert W. Desimone, Jiasheng Guo, Lisa D. Coutts, Sheila I. Hauck, Sam H. Leung, Indranath Ghosh, Douglas Pippin
Dartmouth Scholarship
An account is given of the author’s several approaches to the synthesis of the parent chromophore of phytochrome (1), a protein-bound linear tetrapyrrole derivative that controls photomorphogenesis in higher plants. These studies culminated in enantioselective syntheses of both (2R)- and (2S)-phytochromobilin (4), as well as several 13C-labeled derivatives designed to probe the site of Z,E-isomerization during photoexcitation. When reacted in vitro, synthetic 2R-4 and recombinant-derived phytochrome apoprotein N-C produced a protein-bound chromophore with identical difference spectra to naturally occurring 1.