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David B. Collum
Betty R. Miller Professor
Baker Laboratory, Room 482
1456 Hanshaw Road
dbc6@cornell.edu
607-255-4879
Educational Background
PhD, Columbia University, 1980
MPhil, Columbia University, 1980
MA, Columbia University, 1978
BS, Cornell University, 1977
Website(s)
Overview
The Collum group studies how aggregation and solvation dictate the reactivity and selectivity of organolithium compounds commonly used by synthetic chemists in both academia and the pharmaceutical industry. A combination of spectroscopic, kinetic, and computational methods bridge organic, organometallic, and analytical chemistry.
Keywords
Physical organic chemistry, organolithium chemistry, kinetics and reaction mechanism
Departments/Programs
- Chemistry and Chemical Biology
Graduate Fields
- Chemistry and Chemical Biology
Research
The importance of organolithium reagents in organic chemistry is indisputable. Reports of the effects of solvents, reaction temperatures, additives, internal coordinating functionalities, electrophile structures, and substituents on product distributions pervade the literature. Nevertheless, complexities resulting from aggregation and solvation render our understanding of the origins of the reactivities and selectivities limited at best. Our group investigates the structural and mechanistic basis of selectivity using a range of spectroscopic, kinetic, and computational methods. A number of projects are in collaboration with pharmaceutical process groups.
Courses
Publications
Regioselective Lithium Diisopropylamide-Mediated Ortholithiation of 1-Chloro-3-(trifluoromethyl)benzene: Role of Autocatalysis, Lithium Chloride Catalysis, and Reversibility. Hoepker, A. C.; Gupta, L.; Ma, Y.; Faggin, M. F.; Collum, D. B. J. Am. Chem. Soc. 2011, 133, 7135.
Azaaldol Condensation of a Lithium Enolate Solvated by N,N,N’,N’ Tetramethylethylenediamine: Dimer-Based 1,2-Addition to Imines. De Vries, T. S.; Bruneau, A. M.; Liou, L. R.; Subramanian, H.; Collum, D. B. J. Am. Chem. Soc. 2013, 135, 4214.
Enediolate-Dilithium Amide Mixed Aggregates in the Enantioselective
Alkylation of Arylacetic Acids: Structural Studies and a Stereochemical Model. Ma, Y.; Stivala, C. E.; Wright, A. M.; Hayton, T.; Liang, J.; Keresztes, I.; Lobkovsky, E.; Collum, D. B.; Zakarian, Z. J. Am. Chem. Soc. 2013, 135, 16853.
Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry. Renny, J. S.; Tomasevich, L. L.; Tallmadge, E. H.; Collum, D. B. Angew. Chem., Int. Ed. 2013, 52, 11998.
Solution Structures of Lithium Amino Alkoxides Used in Highly Enantioselective 1,2-Additions. Bruneau, A. M.; Collum, D. B. J. Am. Chem. Soc. 2014, 53, 2885.