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MoreheadFac

Andrew T. Morehead Jr.

Title: Department Chair, Associate Professor, Organic Chemistry
Office: SZ 301
Phone: (252) 328-9702
Email: moreheada@ecu.edu

Asst. Professor, Univ. of Maryland, 1998-2003
NIH Postdoctoral Scholar, Caltech, 1996-1998
PhD Chemistry, Duke University, 1996
AB Chemistry, Harvard University, 1989

Research Overview

Organometallic chemistry bridges the gap between organic and inorganic chemistry, with applications ranging from material science to organic synthesis. My research interests focus on the catalytic applications of transition metal complexes with synthetic organic applications. Summarized below is the current research ongoing in my group, including future plans. Mechanistic and structural studies are necessary parts of this program, and ab initio calculations will be applied when appropriate. One of the points that will be emphasized in my research group will be the development of catalyst systems that are useful at practical temperatures and pressures, and possibly under less than anaerobic or moisture free conditions.

Selected Publications

"Utility of the Nudged Elastic Band Method in Identifying the Minimum Energy Path of an Elementary Organometallic Reaction Step," McPherson, Kate E.; Bartolotti, Libero J.; Morehead, Andrew T.; Sargent, Andrew L. Organometallics (2016), in press.

"Mechanism of Rhodium-Catalyzed Intramolecular Hydroacylation: A Computational Study" Hyatt, I. F. Dempsey; Anderson, Heather K.; Morehead, Andrew T.; Sargent, Andrew L. Organometallics (2008), 27, 135-147.  

"Hydroacylation of 2-Vinyl Benzaldehyde Systems: An Efficient Method for the Synthesis of Chiral 3-Substituted Indanones" Kundu, Kousik; McCullagh, James V.; Morehead, Andrew T. Journal of the American Chemical Society (2005), 127, 16042-16043.

Current Research

The primary project ongoing in the Morehead Group is the synthesis of chiral indanones via intramolecular hydroacylation. As illustrated in Equation 1, we have discovered that the rhodium-catalyzed ring closure of vinylbenzaldehydes proceeds in very high yields and with ee’s as high as 99.4% using BINAP as the chiral ligand.

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During the exploratory work with the above system, we discovered an interesting dimerization (Equation 2). Curiously, addition of an excess of styrene does not result in incorporation of styrene into the tetrahydronaphthalene. Preliminary experiments to elucidate the mechanism have led us to believe that interaction between the pi system of the aromatic ring and the metal may be crucial to this novel form of reactivity.

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Future Plans

Further exploration of the limits of the chiral hydroacylation reaction is planned, as well as mechanistic work designed to elucidate the mechanism of the unusual dimerization we observed.

As mentioned above, we have evidence that there may be an interaction between the pi system of the arene and the metal. We plan to investigate the cyclization of substrates such as that shown in Equation 3, which we should be able to force to either the cycloadduct or the indanone by choice of reaction conditions. Either product is useful in the synthesis of natural products or pharmaceuticals, particularly in a chiral form.

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