Synthetic Methods based on Biphilic Phosphorus Catalysts

项目摘要/摘要 催化科学和技术的进步使制备用于 治疗人类疾病。这个项目的长期目标是开发一大批廉价的 通过定性的形式氧化态循环促进催化转化的非金属催化剂 类似于过渡金属催化。在这一总体目标内，这项提案的主要重点是 P(III)-⇌-P(V)氧化还原电偶中磷基催化剂的设计与应用。 虽然膦作为过渡金属催化的旁观者配体在催化中得到了很好的应用 作为亲核催化剂，本研究介绍了一种新型的组合物磷基催化剂。 探索实现新催化剂所需的结构和电子条件的位置和结构- 通过可逆P(III)⇌P(V)氧化态循环的相关反应性。第一个主要努力是去... 用于直接官能化的酰胺和稳定氧阴离子活化新方法的开发 P(III)⇌P(V)氧化还原反应性。第二个主要工作是发展膦催化的氧原子 转移方法，导致硝基芳烃化合物的还原转化，以提供官能团- 通过形成新的碳-氮键使苯胺化。第三项主要工作涉及消除- P(III)-⇌-P(V)催化N-还原官能化O-原子转移方法的研究进展 包括表现双亲P(III)⇌P(V)氧化还原反应性的新的磷环结构。 这项研究有望为构建Phar-2分子筛提供新的实用催化方法。 与马克学相关的小分子，迎接可持续合成的挑战，以及一种免疫- 证明了对P-块中结构和反应性之间的相互作用的基本理解 为非金属在原子转移、键活化和催化方面的未来发展奠定了基础。带到- 因此，这些结果将推动非金属基氧化还原催化作为一种强有力的手段在医药领域应用。 实践性合成。

PROJECT SUMMARY/ABSTRACT Advances in catalytic science and technology enable the preparation of pharmaceutical agents used to treat human disease. This project has the long-term goal of developing a broad class of inexpensive nonmetal catalysts that promote catalytic transformations via formal oxidation state cycling in qualitative analogy to transition metal catalysis. Within this overarching goal, the primary focus of this proposal is the design and application of phosphorus-based catalysts that function in the P(III)⇌P(V) redox couple. While phosphines are well-established in catalysis as spectator ligands for transition metal catalysis and as nucleophilic catalysts, this research describes innovative phosphorus-based catalysts of novel com- position and structure that explore the structural and electronic conditions required to enable new catalyt- ically-relevant reactivity via reversible P(III)⇌P(V) oxidation state cycling. The first major effort is the de- velopment of new methods for activation of amides and stable oxoanions for direct functionalization via P(III)⇌P(V) redox reactivity. The second major effort is the development of phosphine-catalyzed O-atom transfer methods that result in reductive transformations of nitroarene compounds to furnish functional- ized anilines through the formation of new carbon-nitrogen bonds. The third major effort involves the de- velopment of P(III)⇌P(V)-catalyzed O-atom transfer methods that result in reductive N-functionalization of nitroalkanes, including new phosphacyclic structures that express biphilic P(III)⇌P(V) redox reactivity. The proposed research is expected to yield new practical catalytic methods for the construction of phar- macologically-relevant small molecules that meet the challenges of sustainable synthesis, and an im- proved fundamental understanding the interplay between structure and reactivity in the p-block that will underpin future development of nonmetals for atom transfer, bond activation, and catalysis. Taken to- gether, these outcomes will advance nonmetal-based redox catalysis as a powerful modality in pharma- ceutical synthesis.