Hydrocarbon Oxidation Methods for Synthesis

烃氧化合成方法

• 批准号: 8337059
• 负责人: Maria White
• 金额: $ 29.19万
• 依托单位: UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAIGN
• 依托单位国家: 美国
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-09-26 至 2016-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8337059
• 关键词: Acids; Alkenes; Alkylation; Amino Alcohols; Area; Base Pairing; Biological; Biological Factors; Carbon; Catalysis; Chemicals; Chemistry; Complex; Coupling; Development; Diamines; Future; Glycols; Goals; Hydrocarbons; Hydrogen Bonding; Lead; Ligands; Methods; Molecular; Nature; Nitrogen; Oxidants; Oxygen; Pathway interactions; Pharmacologic Substance; Process; Property; Quinones; Reaction; Research; Skeleton; Sulfoxide; System; Therapeutic; Time; base; catalyst; flexibility; functional group; improved; novel; oxidation; rapid technique; scaffold; tool; wasting

DESCRIPTION (provided by applicant): The architectural and functional group complexity of natural products often confers to them unique modes of biological activity and significant therapeutic value. Despite transformative advances in catalytic methods and strategies for constructing highly complex molecules, the practice of total synthesis still remains a laborious and time intensive pursuit. Consequently, such compounds are rarely sought or evaluated as potential therapeutics. Historically, the development of new synthetic methods has had a profound impact on the efficiency of complex molecule synthesis. New reaction classes that lead to fundamentally novel reactivity stand to promote the largest advances in this regard. As a guide, we can look towards Nature¿s synthetic strategies that systematically employ C-H oxidation and complexity generating C-C bond forming reactions. This proposal seeks to establish allylic C-H bonds as a new functional group for widespread use in complex molecule synthesis. To achieve this goal we will exploit a highly versatile ¿-allyPd intermediate, accessed through allylic C-H cleavage, and develop general strategies by which it can participate in diverse reaction types with consistently high selectivities. Collectively, we expect these Pd(II)-catalyzed allylic C-H functionalization reactions to become fundamental tools for streamlining the synthesis of important structural motifs found in natural products, bioactive compounds, and medicinal agents. Moreover, the general principles that emerge from this approach will be broadly applicable to the field of C-H activation.) PUBLIC HEALTH RELEVANCE: The objective of this research is to discover and develop catalytic reactions that establish the allylic C- H bond as a new functional group for widespread use in the synthesis of structural motifs found in natural products, bioactive compounds, and medicinal agents.)

描述（由申请人提供）：天然产物的结构和功能群复杂性通常赋予它们独特的生物活性模式和显著的治疗价值。尽管在构建高度复杂分子的催化方法和策略方面取得了革命性的进步，但全合成的实践仍然是一项艰苦而耗时的追求。因此，很少寻求或评估这类化合物作为潜在的治疗药物。历史上，新合成方法的发展对复杂分子合成的效率产生了深远的影响。新的反应类别导致了从根本上新颖的反应性，这将促进这方面的最大进步。作为指导，我们可以看看自然界的合成策略，系统地利用碳氢氧化和复杂性生成碳氢键形成反应。本提案旨在建立烯丙基C-H键作为一个新的官能团，广泛应用于复杂分子的合成。为了实现这一目标，我们将开发一种高度通用的¿-allyPd中间体，通过烯丙基C-H裂解获得，并制定一般策略，使其能够以一贯的高选择性参与不同的反应类型。总的来说，我们期望这些Pd（II）催化的烯丙基C-H功能化反应成为简化天然产物、生物活性化合物和药物中重要结构基序合成的基本工具。此外，从这种方法中产生的一般原理将广泛适用于C-H活化领域。