gas phase calculations of ether synthesis from...
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Gas Phase Calculations of Ether Synthesis from
Peroxy-AlkylsTristan Truttmann, Ruth Pardini, and Rebecca Meier
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● Introduction○ Ethers in industry, nature○ Traditional synthesis○ A new synthesis
● Computational procedure○ Recalculations and struggles
● Results○ Quantitative and Qualitative
● Conclusions
Overview
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Industrial Ethers
● Common chemical feedstock● Used in starting fluid
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Ethers in the Natural World
Maito
Maitotoxin
● A toxin produced by dinoflagellates found in the maito fish
● 0.14µg lethal in mice
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Ethers in the Natural WorldBrevetoxins
● Series of toxins produced from a dinoflagellate in the Gulf of Mexico
● Responsible for the toxicity of the Florida Red Tide
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Tetrodotoxin● Present in puffer fish● Responsible for the intoxicating effects and
danger of the Japanese cuisine “fugu”
Ethers in the Natural World
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Traditional Ether Preparation
● All common variations of ether synthesis use nucleophilic oxygen, electrophilic carbon.
● The Williamson Ether synthesis epitomizes this
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A New Route for Ether Synthesis
Willand-Charnley synthesis● Electrophilic oxygen via peroxide● Nucleophilic carbon via organometallic
Willand-Charnley et al., “Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides,” 2014
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Our Project
Goal: Provide a limited computational analysis of this of Willand-Charnley’s synthesis method
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Our Project: Original Calculations
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Additional Calculations Increasing Bulk
Metal R1 R2 R3Li Tert-butyl Tert-butyl Methyl
Na Tert-butyl Tert-butyl Methyl
K Tert-butyl Tert-butyl Methyl
Li THP Tert-butyl Methyl
Na THP Tert-butyl Methyl
K THP Tert-butyl Methyl
Li Tert-butyl Methyl Tert-butyl
Na Tert-butyl Methyl Tert-butyl
K Tert-butyl Methyl Tert-butyl
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Computation● Level of Theory: B3YLP● Basis Set: 6-31+G(d,p)● Calculation types
o Opt + Vib Freqo Saddle Calculationo Transition State Optimizationo Forward and Reverse IRC
Locating structures
Checking structures
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Stage I: Structures
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Stage II: Structures
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Stage II: Difficulties
Original Conformer“Axial”
Located using Opt + Vib Freq
Lower Energy Conformer“Equatorial”
Located using IRC calculations
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Stage III- Transition State
● R3 partially binds to Oxygeno R-M-O angle decreases
● O-O bond lengthens by ~0.5 Å
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Stage IV: Structures
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Stage V: Structures
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Discussion- Trends
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Discussion-Trends
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Discussions-Trends
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Discussion-Trends
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Conclusion● Gas phase versus solvent calculations
o Quantitative results by themselves will not be very applicable to the laboratory.
● However, trends will likely hold trueo We expect all the trends discussed on this slideshow
to hold true on analogous solvent calculations and thus in the laboratory.
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Future Work● Expand on bulk calculations● Solvent calculations● Cyclic ethers● Highly Electrophilic Peroxides to overcome
ring strain
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Acknowledgements● Keith Kuwata for providing us with the
intellectual tools to tackle this project● Midwestern Undergraduate
Computational Chemistry Consortiumfor providing computational resources
● Patrick Dussault for discovering this chemistry in the lab and working with us on this project
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References:● Nakata, T. “SnI2-induced reductive cyclization for the synthesis of cyclic ethers and applications
in natural product synthesis.” Chemical Society Reviews 2010, 39, 1955-1972.● Willand-Charnley, R.; Puffer, P. W.; Dussault, P. H. “Oxacycle Synthesis via Intramolecular
Reaction of Carbanions and Peroxides.” Journal of the American Chemical Society 2014, 136, 5821-5823.
● Karas, L.; Piel W. J. “Ethers.” In Kirk-Othmer Encyclopedia of Chemical Technology, 4; Kroschwitz, J. I., Howe-Grant, M.; John Wiley & Sons: New York, 1998.
● Rao, A. S.. “Addition Reactions with Formation of Carbon-Oxygen Bonds: (i) General Methods of Epoxidation.” In Comprehensive Organic Synthesis: Selectivity, Strategy & Efficiency in Modern Organic Chemistry, Volume 7; Ley S. V.; Pergamon Press: New York, 1991; 3.1.2.
● Politzer, P. “Bond Energy” In Macmillan Encyclopedia of Chemistry, Volume 1; Lagowski, J. J.; Macmillan Refference USA: New York, 1997.
● Robert J. Ouellette, J. David Rawn. Organic Chemistry Study Guide: Key Concepts, Problems, and Solutions, 1st ed.; Elsevier Inc: Amsterdam, 2014; Chapter 3.
● WebMO, Schmidt, J.R.; Polik, W.F. WebMO Enterprise, version 13.0; WebMO LLC: Holland, MI, USA, 2013; http://www.webmo.net (accessed Nov- Dec, 2014)
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References:● Gaussian09, Revision C.01,M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci,G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian,A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada,M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima,Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr.,J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers,K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand,K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross,V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski,R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. V oth,P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2010.
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References: sources of images● http://en.wikipedia.org/wiki/Fugu● http://en.wikipedia.org/wiki/Tetrodotoxin● http://en.wikipedia.org/wiki/Brevetoxin● http://en.wikipedia.org/wiki/Maitotoxin● http://en.wikipedia.org/wiki/Tetraodontidae● http://en.wikipedia.org/wiki/Diethyl_ether● http://en.wikipedia.org/wiki/Striated_surgeonfish● http://www.zoro.com/i/G4579443/?utm_source=google_shopping&utm_medium=cpc&utm_camp
aign=Google_Shopping_Feed&gclid=CjwKEAiAk8qkBRDOqYediILQ5BMSJAB40A5UAJoN-cIFkvYdIOsL3JdHCkmXjjn4w0gWZMwW0ApitxoCypjw_wcB