RUI: Transition-Metal Templated Radical Reactions

Middlebury College, Middlebury VT

Investigators

Abstract

This proposal addresses the feasibility of using radical processes to carry out molecular transformations on several classes of organometallic complexes, leading to the development of synthetic methodology to carry out transformations that would otherwise prove difficult, if not impossible, using known reactions. Benzene, normally unreactive toward simple alkyl radicals, will be activated towards alkyl radical attack through complexation with transition metals, leading to new methods for elaborating this simple substance into more complex and useful materials. A systematic study of the radical reactions of cyclobutadieneiron tricarbonyl, will provide new means of incorporating cyclobutadiene in organic molecules in order to take advantage of its high reactivity. Organic molecules bearing an unpaired electron ("radicals") are frequently very reactive. However, they do not react in a useful manner with certain types of molecules, precluding the use of such reactions to assist in the synthesis of more complex structures. With the support of a Research at Undergraduate Institutions award from the Organic and Macromolecular Chemistry Program, Professor Jeffrey H. Byers, of the Department of Chemistry and Biochemistry at Middlebury College, is exploring the feasibility of using interactions with metal ions to facilitate such transformations. Benzene, one of the most common feedstock chemicals, is normally unreactive with simple alkyl radicals. New methods for activating benzene towards alkyl radical attack through use of its complexes with transition metals will be explored, leading to new methods for elaborating this very simple substance into more complex and useful materials. Cyclobutadiene is so unstable that it only exists in the free state under the most exotic of conditions. It has been known to exist in a stable and readily handled form upon complexation with iron tricarbonyl. While this molecule has piqued the curiosity of organic chemists for over 35 years, it has been used only sparingly in complex synthesis, in part due to the lack of methods for its subsequent elaboration into more complex and useful substances. By examining the radical reactions of cyclobutadieneiron tricarbonyl, Professor Byers, working with a team of undergraduate research students, will explore new means of incorporating cyclobutadiene in organic molecules in order to take advantage of its high reactivity. Since transition metal-catalyzed and radical processes are of exceptional importance to the chemical industry, this work could open up new avenues for the efficient generation of complex molecules of broad applicability and importance.