Hydrocarbon Oxidation Methods for Synthesis

描述(由申请人提供)：天然产品的结构和官能团的复杂性往往赋予它们独特的生物活性模式和重要的治疗价值。尽管构建高度复杂分子的催化方法和策略取得了革命性的进展，但全合成的实践仍然是一个费力和耗时的追求。因此，这类化合物很少被作为潜在的治疗药物来寻找或评估。从历史上看，新的合成方法的发展对复杂分子的合成效率产生了深远的影响。导致从根本上新颖的反应性的新的反应类别将促进这方面的最大进展。作为指导，我们可以期待《自然》S的合成策略，该策略系统地利用C-H氧化和复杂性产生C-C键形成反应。这一提议旨在建立烯丙基C-H键作为一种新的官能团，在复杂分子合成中得到广泛应用。为了实现这一目标，我们将开发一种用途广泛的β-allyPd中间体，通过烯丙基C-H裂解获得，并开发通用策略，使其能够以一贯的高选择性参与不同类型的反应。总的来说，我们期望这些钯(II)催化的烯丙基C-H官能化反应成为简化天然产物、生物活性化合物和药物中发现的重要结构基序合成的基本工具。此外，这种方法产生的一般原则将广泛适用于C-H活化领域。)

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.)