ACS Award in Organometallic Chemistry

Sponsored by Dow Chemical Co. Foundation

John F. Hartwig, 41, professor of chemistry at Yale University, is being recognized for his contributions to the application of organometallic chemistry and mechanistic principles to the development of new synthetic organic chemistry methods. Members of both the inorganic and organic chemistry communities praise him for his productivity, creativity, and intellectual depth.

"John has pioneered an impressive array of new and useful reactions not by screening, but by creative and careful thought with sophisticated mechanistic analysis," explains Yale chemistry colleague Robert H. Crabtree. Hartwig's palladium coupling catalysts are used in both academic and industrial synthetic research. Expanding the impact of his work even further, he has devised chiral ligands to adapt his methods to enantioselective reactions.

"We try to pick projects where we will have an impact on synthesis and also reveal new organometallic chemistry," Hartwig says. Beyond just being "good puzzles," deciphering reaction mechanisms is key to improving catalytic processes, he adds. "Catalyst development is dynamic, but if we can make conceptual advances, these principles remain regardless of what the best catalyst is today or tomorrow."

Hartwig and coworkers have developed a series of Pd-catalyzed amination and ether-forming reactions of aryl halides and sulfonates. These carbon-heteroatom bond-forming processes, such as Buchwald-Hartwig amination, have found wide-ranging application in preparing pharmaceuticals and electronic materials. He has also developed an extremely efficient α-arylation process for ketones, esters, amides, and malonates. Most recently, he has developed highly efficient and novel enantioselective allylic amination and etherification reactions.

Among Hartwig's other discoveries were the first N-H activation of ammonia by monomeric late-transition-metal complexes and the first β-elimination from monomeric amido-metal complexes. In parallel with the development of C-N and C-O coupling processes, he also discovered some of the first complexes that undergo reductive elimination reactions to form the C-N and C-O bonds in amines and ethers. These discoveries are crucial for a detailed understanding of the catalytic mechanisms and the future design of catalytic processes.

Other impressive work includes the first thermal catalytic functionalization of alkanes at their termini using rhodium complexes as the catalysts, says Iwao Ojima, professor of chemistry at the State University of New York, Stony Brook. Although catalytic C-H activation of alkanes has been studied extensively, there is no practical example of a nonphotochemical process.

Beyond its practical impact, Hartwig's research has reoriented the thrust of organometallic chemistry itself, says Robert G. Bergman, professor of chemistry at the University of California, Berkeley, and one of Hartwig's Ph.D. advisers. "An important aspect of his work is a commitment to put sustained effort into the synthesis and full characterization of novel reactive organometallic complexes and into the fundamental understanding of the mechanisms of the reactions he is working on," Bergman says.

Hartwig received his undergraduate degree from Princeton University in 1986. In 1990, he received his doctorate at Berkeley, under the direction of Bergman and chemistry professor Richard A. Andersen. After postdoctoral work with Stephen J. Lippard at Massachusetts Institute of Technology, he moved to Yale in the summer of 1992.

He received the Thieme-IUPAC Prize in Synthetic Organic Chemistry, the Solvias Ligand Prize, and Chemical Abstracts Service Science Spotlight Award in 2004. In 2003, he received the Leo Hendrik Baekeland Award and, before that, an Arthur C. Cope Scholar Award.

The award address will be presented before the Division of Organic Chemistry.—Ann Thayer