Dr. Jeffrey Mighion
"Selective Functionalization of Carbon-Hydrogen Bonds"
Carbon-hydrogen bonds (C鈥揌 bonds) are ubiquitous in organic molecules and the selective conversion of these C鈥揌 bonds into carbon-carbon, carbon-nitrogen, carbon-oxygen, and other types of bonds is a major area of chemical research within the organic community.1 Utilization of C鈥揌 bonds as synthetic handles to build molecular complexity is a challenge due to the number of C鈥揌 bonds present in organic compounds and their usually low reactivity, yet is also rewarding as this allows for utilization of cheap, renewable starting materials and simplification of synthetic strategy.2 There are three main classes of reactions that many of the C鈥揌 functionalization strategies fall into:1) C鈥揌 activation by generation of an organometallic species from a C鈥揌 bond; 2) group transfer chemistry which usually takes place at an electrophilic low-valent ligand on the metal (i.e. carbenoid, nitrenoid, oxo); and 3) homolytic cleavage, C鈥� H abstraction or radical methodology. Our research over the REU summer focuses on the second class of reactions, group transfer chemistry. Specifically, how do we create these reactive metalloids and how can we utilize and access new metalloid species?
REU students will synthesize new organometallic catalyst, test their ability to catalyze group transfer reactions and explore the reactivity of these new catalysts with the goal of developing novel and useful reactivity. The use of modern organic laboratory chemistry skills, spectroscopy, and synthetic design will be taught over the course of the REU.
1) (a) Davies, H. M. L.; Manning, J. R. Nature 2008, 451, 417. (b) Lewis, J. C.; Bergman, R. G.; Ellman, J. A. Acc. Chem. Res. 2008, 41, 1013. (c) Zhang, S.-Y.; Zhang, F.-M.; Tu, Y.-Q Chem. Soc. Rev. 2011, 40, 1937. (d) Newhouse, T.; Baran, P. S. Angew. Chem. Int. Ed. 2011, 50, 3362. (e) Zalatan, D. N.; Du, B. J Top. Curr. Chem. 2010, 292, 347. (f) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147. (g) Davies, H. M. L.; Morton, D. J. Org. Chem. 2016, 81, 343.
2) (a) Br眉ckl, T.; Baxter, R. D.; Ishihara, Y.; Baran, P. S. 鈥�Acc. Chem. Res. 2012, 45, 826. (b) Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976. (c) Davies, H. M. L.; Denton, J. R. Chem. Soc. Rev. 2009, 38, 3061. (d) Godula, K.; Sames, D. Science, 2006, 312, 67.
