New Avenues of TMM Diradical Chemistry

TMM双自由基化学的新途径

• 批准号: 0200855
• 负责人: R. Daniel Little
• 金额: --
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-15 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0200855&HistoricalAwards=false
• 关键词: New; Avenues; TMM; Diradical; Chemistry

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.

在有机化学和高分子化学项目的支持下，加州大学圣巴巴拉分校化学和生物化学系的R.Daniel Little教授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。利特尔教授利用双氮烯作为双自由基前驱体，探索导致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选择性形成的因素。对称和不对称的1，3-二基自由基阳离子是7元和8元环化合物组装的研究对象，也是阳离子自由基平衡和反冲伴随氮从二叠氮烯损失的机理分析的主题。许多具有有趣的化学或生物活性的有机化合物都含有7元或8元的原子环。开发有效的技术来合成这类环状化合物仍然很有兴趣，特别是考虑到小环(5元和6元)化合物通常具有更高的稳定性。加州大学圣巴巴拉分校化学和生物化学系的R.Daniel Little教授正在开发新的反应，允许选择性地合成7元和8元环化合物，并研究导致这些反应选择性的因素。