Dr. David M. Birney
Education: Ph.D., Yale University, 1987; Postdoctoral Study, University of California, Los Angeles; Guest Professor, ETH - Zurich, Fall 2008
Research Area: Physical Organic & Mechanistic Chemistry
Office: Chemistry 232-C
Principal Research Interests
In our group, we use high level ab initio and density functional calculations to provide fundamental insights into two classes of reactions, pseudopericyclic and pericyclic. We then design and conduct experiments to test the predictions of these calculations. The synergy between theory and experiment has provided insights and research directions that would not be possible from either alone.
The "conventional wisdom" of the orbital symmetry rules tells an organic chemist what to expect from a pericyclic reaction. Pseudopericyclic reactions violate all of these expectations of a pericyclic reaction, yet strictly speaking they are orbital symmetry allowed. The fundamental difference between the two is that in a pseudopericyclic reaction, there is not orbital overlap around the ring of breaking and forming bonds. This allows their transition states to have a planar geometry, and, often, very low activation barriers.The difference between a planar pseudopericyclic transition state and a non-planar pseudopericyclic one is illustrated in two animations of these reaction pathways. The dramatic differences in geometries between them are summarized below.
Familiar Pericyclic Reactions
Cyclic orbital overlap
Non-planar, non-least motion transition states
Pericyclic reactions can be allowed or forbidden, depending on the number of electrons
Concerted pericyclic reactions have lower barriers than stepwise alternatives. Barriers are due to enforced electron-electron repulsion
Novel Pseudopericyclic Predictions
Disconnections in orbital overlap
Planar (or nearly planar) transition states
All pseudopericyclic reactions are allowed; there are no anti-aromatic transition states
Pseudopericyclic reactions can have lower barriers than pericyclic alternative. There is no enforced electron-electron repulsion
- "Experimental and Computational Studies on the [3,3]- and [3,5]-Sigmatropic Rearrangement of Acetoxycyclohexadienones; a Non-ionic Mechanism for Acyl Migration." Shikha Sharma, Trideep Rajale, David B. Cordes, Fernando Hung-Low, David M. Birney, J. Am. Chem. Soc., 2013, 135, 14438-14447 .
- "Optimizing esterification of safflower, cottonseed, castor and used cottonseed oils." Tina P. Thomas, David M. Birney, Dick L. Auld, Industrial Crops and Products, 2013, 41, 102-106."
- Selective Oxygenation of Olefins with Hydrogen Peroxide Catalyzed by Iron(II) Bipyridine Included in NaY Zeolite under Visible Light Irradiation." Yanjun Ren, Wanhong Ma, Yanke Che, Xuefeng Hu, Xinzhi Zhang, Xinhua Qian and David Birney, Journal of Photochemistry and Photobiology A: Chemistry, 2013, 266, 22-27.
- "Viscosity reduction of castor oil esters by the addition of diesel, safflower oil esters and additives." TinaP. Thomas; David M. Birney and Dick L. Auld, Industrial Crops and Products 2012, 36, 267-270.
- "The Potential Energy Surface for (Retro-)Cyclopropanation – Metathesis with a Cationic Gold Complex." Alexey Fedorov; Laurent Batiste; Andreas Bach; David Birney; Peter ChenJ. Am. Chem. Soc. 2011, 133(31), pp 12162-12171.
- “Theory, Experiment and Unusual Features of Potential Energy Surfaces of Pericyclic and Pseudopericyclic Reactions with Sequential Transition Structures.” David Martin Birney;Curr. Org. Chem. 2010, 14(15), 1658-1668.
- "Multiphoton Infrared Initiated Thermal Reactions of Esters: Pseudopericyclic Eight-Centered cis-Elimination" Hua Ji; Li Li; Xiaolian Xu; Sihyun Ham; Loubna A. Hammad; David M. Birney; J. Am. Chem. Soc. 2009, 131, 528-537.
- “Sodium carbonate as a solid-phase reagent for the generation of acetylketene.” Kelcey Bell; Dhandapani V. Sadasivam; Indra Reddy Gudipati; Hua Ji; David Birney; Tetrahedron Lett. 2009, 50, 1295–1297.
- “Cyclohexane Isomerization. Unimolecular Dynamics Of The Twist-Boat Intermediate.” Khatuna Kakhiani; Upakarasamy Lourderaj; Wenfang Hu; David Birney and William L. Hase J. Phys. Chem. A. 2009, 113, pp 4570–4580.
- "Microwave generation and trapping of acetylketene." Gudipati, I. R.; Sadasivam, D. V.; Birney, D. M. Green Chem. 2008, 10, 283-285.
- "A Computational Study of the Formation and Dimerization of Benzothiet-2-one." Sadasivam, D. V.; Birney, D. M. Org. Lett. 2008, 10, 245-248.
- "Photochemical Dehydration of Acetamide In a Cryogenic Matrix.", Duvernay, F.; Chatron-Michaud, P.; Borget, F.; Birney, D.; Chiavassa, T. Phys. Chem. Chem. Phys. 2007, 9, 1099.
- "Stopped-flow kinetics of tetrazine cycloadditions; Experimental and computational studies towards sequential transition states.”, Sadasivam, D. V.; Prasad, E.; Flowers II, R. A.; Birney, D. M. J. Phys. Chem. 2006, 110(4), 1288-1294. An invited contribution to the William Hase Festschrift.
- "A Theoretical Study of the [4 + 4] Dimerization of Thioformylketene.", Sadasivam, D. V.; Birney, D. M. Org. Lett. 2005, 7, 5817-5820.
- "Experimental Support For Planar Pseudopericyclic Transition States In Thermal Cheletropic Decarbonylations.”, Wei, H.-X.; Zhou, C.; Ham, S.; White, J. M.; Birney, D. M. Org. Lett. 2004, 6, 4289-4292.
- "Experimental and Theoretical Studies of the Dimerizations of Imidoylketenes.”, Zhou, C.; Birney, D. M. J. Org. Chem. 2004, 69, 86-94.
- "Nitrosation of Amides Involves a Pseudopericyclic 1,3-sigmatropic Rearrangement.”, Birney, D. M. Org. Lett. 2004, 6, 851-854.
- "5-Didehydro-3-picoline Diradicals from Skipped Aza-Enediynes: Computational and Trapping Studies of an Aza-Myers-Saito Cyclization.", Feng, L.; Kumar, D.; Birney, D. M.; Kerwin, S.M. Org. Lett. 2004, 6, 2059–2062.
- "The Stereochemistry of the Thermal Cheletropic Decarbonylation of 3-Cyclopentenone as Determined by Multiphoton Infrared Photolysis/Thermolysis." Unruh, G. R.; Birney, D. M. J. Am. Chem. Soc. 2003, 125, 8529 – 8533.
- "Sequential Transition States and the Valley-ridge Inflection Point in the Formation of a Semibullvalene." Zhou, C.; Birney, D. M. Org. Lett. 2002, 4, 3279-3282.
- "A DFT Study Clarifying the Reactions of Conjugated Ketenes with Formaldimine. A Plethora of Pericyclic and Pseudopericyclic Pathways." Zhou, C.; Birney, D. M., J. Am. Chem. Soc. 2002, 124, 5231-5241.
- "Structural Investigations Into the Retro Diels Alder Reaction. Experimental and Theoretical Studies." Birney, D.; Lim, T. K.; Peng, J.; Pool, B. R.; White, J. M. J. Am. Chem. Soc. 2002, 124, 5091-5099.