Philip E. Eaton Professor Emeritus

Born New York, New York, 1936.
Princeton University, A.B., 1957.
Harvard University, Ph.D., 1961.
University of California at Berkeley, 1960-1962.
The University of Chicago, Professor, 1962-.

Accolades

Fellow, American Association for the Advancement of Science.
1999 Yamada Award, Japan.
1997 American Chemical Society Arthur C. Cope Scholar Award.
1997 Frank Burnett Dains Lecturer, University of Kansas.
1995 Alan Berman Research Publication Award.
1991 American Chemical Society National Organic Symposium Lecturer.
1990 National Science Council Distinguished Lecturer, Republic of China.
1988 French Speaking Universities of Switzerland Lectureship.
1985 Alexander von Humboldt Prize.
1975 Rohm and Haas Research Award.
1963-1969 Alfred P. Sloan Fellow.

OFFICE: 929 E. 57th St., GCIS E 203, Chicago, IL 60637

PHONE: (773)702-7088

FAX: (773)702-0805

E-MAIL: eaton@uchicago.edu

WEB: http://none

RESEARCH INTERESTS:

My group's research interests are focused on the synthesis and examination of new ring systems specifically designed as probes into the effects of molecular geometry on bonding, reactivity, strain, etc. In the course of our work we were first to synthesize cubane, pentaprismane, [2.2.2]propellane, the [n.2.2.2]paddlanes, and many other highly strained "unnatural" compounds. These systems have given us special opportunities to study the behavior of exceptionally strained molecules vis-a-vis their propensity for rearrangement and reaction.


Cubane is the most highly strained, kinetically stable ring system available in quantity. We have used it as the source of even more highly strained compounds including 1(9)-homocubene (the most highly twisted olefin), cubene, (the most highly pyramidalized olefin), and such intriguing species as 1,4-dehydrocubane, cubyl cation (the "least likely" cation), and the cubylcarbinyl radical (the fastest rearranging saturated radical). These have "record" properties and as such have proven to be of fundamental importance in developing an understanding of bonding in strained systems.


As the geometric requirements of such compounds are far from ordinary, tactical synthesis is an exceptional challenge. Much of our work, therefore, is on the development and application of new synthesis methods and techniques. Most recently we have developed new bases capable of directly magnesiating CH groups with pKa<35; this has opened the way to systematic substitutions on strained systems. We are working now on how to do this with high enantiospecificity.


Cubanes and other unnatural products offer interesting practical applications as diverse as anti-viral agents, explosives, high-refractive index lenses, liquid crystals, specialty polymers, and fuel additives. We recently completed the synthesis of octanitrocubane (ONC)­ the first new example of a fully nitrated compound to be made in the last 20 years ­- there are only six others. We are now working on the synthesis of the still unknown dinitroacetylene. Once it is made, we want to find how to achieve its predicted and strongly exothermic tetramerization to ONC.


Selected References

A New Approach to Substituted Cyclobutanes: Direct β- Deprotonation/Magnesiation of Cyclobutane Carboxamides, SynLett, 9, 1275-1278 (2003).

BuMgNiPr2: A New Base for Stoichiometric, Position-Selective Deprotonation of Cyclopropane Carboxamides and Other Weak CH Acids, Angew. Chemie Int. Ed. Engl., 41, 2169-2171 (2002).

Nitroacetylene: HCCNO2, Synthesis, 14, 2013-2018 (2002)

Octanitrocubane: A New Nitrocarbon. Propellants, Explosives, Pyrotechnics, 27, 1-6 (2002).

Hepta- and Octanitrocubane, Angew. Chemie. Int. Ed. Engl., 39, 401-404 (2000).

Polynitrocubanes: Advanced High-Density, High-Energy Materials, Adv. Mat., 12, 1143-1148 (2000).

Building with Cubane-1,4-diyl. Synthesis of Aryl Substituted Cubanes, p-[n]Cubyls, and Cubane Separated Bis-Arenes. J. Am. Chem. Soc., 121, 4111 (1999).