RUI: Transition-Metal Templated Radical Reactions

该提案提出了使用自由基过程对几种有机金属配合物进行分子转化的可行性，从而导致合成方法的发展，否则使用已知反应进行转化将被证明是困难的，如果不是不可能的。苯通常对简单的烷基自由基不起反应，但通过与过渡金属的络合作用，它对烷基自由基的攻击起了激活作用，从而产生了将这种简单物质精制成更复杂、更有用的材料的新方法。对环丁二烯三羰基铁自由基反应的系统研究，将为环丁二烯在有机分子中的结合提供新的手段，以充分利用其高活性。带有未配对电子（“自由基”）的有机分子通常非常活泼。然而，它们不能与某些类型的分子有效地反应，这就妨碍了利用这些反应来辅助合成更复杂的结构。在有机和大分子化学项目的本科机构研究奖的支持下，米德尔伯里学院化学和生物化学系的杰弗里·h·拜尔斯教授正在探索利用与金属离子的相互作用来促进这种转化的可行性。苯是最常见的原料化学品之一，通常不与简单的烷基自由基反应。我们将探索利用苯与过渡金属的配合物活化苯以抵抗烷基自由基攻击的新方法，从而找到将这种非常简单的物质加工成更复杂和有用的材料的新方法。环丁二烯非常不稳定，它只在最特殊的条件下以自由态存在。已知它在与三羰基铁络合后以稳定和易于处理的形式存在。35年来，这种分子一直激发着有机化学家的好奇心，但在复杂的合成中很少使用它，部分原因是缺乏将其加工成更复杂、更有用的物质的方法。通过研究环丁二烯铁三羰基的自由基反应，拜尔斯教授将与一组本科生一起探索将环丁二烯结合到有机分子中的新方法，以利用其高反应性。由于过渡金属催化和自由基过程对化学工业非常重要，这项工作可以为有效产生具有广泛适用性和重要性的复杂分子开辟新的途径。

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.