New Avenues of TMM Diradical Chemistry

在有机和高分子化学项目的支持下，R。圣巴巴拉的加州大学化学与生物化学系的丹尼尔·利特尔正在研究三亚甲基甲烷双自由基和1，3-二基自由基阳离子的反应化学。使用二氮烯作为双自由基前体，Little教授正在探索选择性形成8元环碳环化合物或其6元环异构体以及含氧和含氮杂环类似物的因素。对称和不对称的1，3-二基阳离子自由基是研究7-和8-元环化合物组装以及阳离子自由基平衡和反冲的机理分析的主题。许多显示出有趣的化学或生物活性的有机化合物含有7-或8-元环原子。用于合成此类环状化合物的有效技术的开发仍然具有极大的兴趣，特别是鉴于较小环（5元和6元）化合物通常具有更大的稳定性。R教授圣巴巴拉的加州大学化学和生物化学系的丹尼尔利特尔正在开发新的反应，允许选择性合成7元和8元环化合物，并研究这些反应的选择性的因素。

With the support of the Organic and Macromolecular Chemistry Program, Professor R. Daniel Little, of the Department of Chemistry and Biochemistry at the University of California, Santa Barbara, is studying the reaction chemistry of trimethylenemethane diradicals and 1,3-diyl radical cations. Using diazenes as diradical precursors, Professor Little is exploring the factors responsible for selective formation of 8-membered ring carbocyclic compounds or their 6-membered ring isomers, as well as oxygen- and nitrogen-containing heterocyclic analogs. Symmetrical and unsymmetrical 1,3-diyl radical cations are the subjects of studies relating to the assembly of 7- and 8-membered ring compounds as well as mechanistic analyses of cation radical equilibration and recoil accompanying loss of nitrogen from diazenes.Many organic compounds which display interesting chemical or biological activity contain 7- or 8-membered rings of atoms. The development of efficient techniques for the synthesis of such cyclic compounds remains of great interest, particularly in light of the generally greater stability of smaller-ring (5- and 6-membered) compounds. Professor R. Daniel Little, of the Department of Chemistry and Biochemistry at the University of California, Santa Barbara, is developing new reactions allowing the selective synthesis of 7- and 8-membered ring compounds and studying the factors responsible for the selectivity of these reactions.