Reactivity and Applications of a New Type of Diene

新型二烯的反应活性及应用

• 批准号: 0518434
• 负责人: Erik Sorensen
• 金额: $ 42万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2008-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0518434&HistoricalAwards=false
• 关键词: Reactivity; Applications; New; Type; Diene

This project focuses on the design and synthesis of a new type of 1,3-diene, containing a functionalized hydrazino group at position 1, and on the exploration of its intermolecular Diels-Alder reactions with various electron deficient alkenes and heterodienophiles. In a subsequent step, cleavage of two protecting groups on one of the nitrogen atoms triggers a sequential fragmentation and a suprafacial 1,5-sigmatropic rearrangement of hydrogen with loss of a molecule of nitrogen. This thermodynamically driven process, which presumably passes through an allylic diazene intermediate, gives rise to a rearranged cyclohexene with a remote stereochemical relationship. The two-stage strategy is thus founded on the powerful Diels-Alder cycloaddition as a ring forming process and the facility of allylic diazene rearrangements. The unique chemistry of the 1-hydrazinodienes provides direct access to stereochemically complex cyclohexenes that would be difficult to construct by alternative synthesis strategies.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Erik J. Sorensen of the Department of Chemistry at Princeton University. Since its initial description in 1928, the Diels-Alder reaction has evolved into one of the most important structure building processes in the field of chemical synthesis. The novel reactants targeted by Professor Sorensen and his students are easily synthesized from simple, commercially available compounds, and they enable short syntheses of complex ring systems that would be challenging to construct by alternative strategies. These studies are expected to have a strong impact on the field of chemical synthesis, providing chemists with an alternative way of perceiving and utilizing the Diels-Alder reaction in the planning and execution of organic syntheses. In addition, this reaction chemistry will potentially yield structurally diverse compounds for use in complex chemical synthesis and medicinal chemistry.

该项目的重点是设计和合成一种新型的1，3-二烯，在1位含有官能化肼基，并探索其与各种缺电子烯烃和亲杂二烯体的分子间Diels-Alder反应。在随后的步骤中，在一个氮原子上的两个保护基团的裂解引发氢的顺序断裂和超面1，5-σ迁移重排，同时损失一个氮分子。这是一个由催化剂驱动的过程，可能通过烯丙基二氮烯中间体，产生一个具有远程立体化学关系的重排环己烯。因此，两阶段的战略是建立在强大的狄尔斯-阿尔德环加成作为一个环的形成过程和设施的烯丙基重氮烯重排。1-肼基二烯的独特化学性质提供了直接获得立体化学复杂的环己烯的途径，这些环己烯很难通过其他合成策略来构建。有了这个奖项，有机和大分子化学计划将支持普林斯顿大学化学系的Erik J. Sorensen博士的研究。自1928年首次描述以来，Diels-Alder反应已经发展成为化学合成领域中最重要的结构构建过程之一。索伦森教授和他的学生所针对的新型反应物很容易从简单的市售化合物合成，并且它们能够短时间合成复杂的环系统，这将是通过替代策略构建的挑战。这些研究预计将对化学合成领域产生重大影响，为化学家在有机合成的规划和执行中感知和利用Diels-Alder反应提供另一种方式。此外，这种反应化学将潜在地产生用于复杂化学合成和药物化学的结构多样的化合物。