Catalysis by Phospino Gold Complexes: Application in Synthesis and Photoredox Transformations

膦金配合物的催化：在合成和光氧化还原转化中的应用

• 批准号: RGPIN-2015-05384
• 负责人: Barriault, Louis
• 金额: $ 5.39万
• 依托单位: University of Ottawa
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=613519
• 关键词: Catalysis; Phospino; Gold; Complexes; Application

The development of new synthetic methods for the formation of carbon-carbon bond is of paramount importance for the efficient synthesis of molecules having important application in medicine and material science. Most of the traditional chemical reactions to construct carbon-carbon bonds have a poor atom economy i.e. the amount of reagents does not equal the amount of all products produced thus leading to a waste of atoms. The ever-increasing emphasis being placed on sustainability and environmental problems, the need for efficient and waste-minimizing processes is becoming more and more important. Homogenous catalysis by transition metals has emerged as one of the most important field in organic chemistry. In the recent years, homogenous catalysis by coinage metals has received considerable attention by the scientific community. For instance, the high affinity of Au(I/III) salts for alkynes and allenes in the presence of many other functional groups, combined with its ability to stabilize cationic charge provide tremendous opportunities for the discovery novel and useful reactions. In addition, phosphino dimeric gold complexes can be used as photocatalyst owing to their high-energy and long-lived excited states and stronger reduction potentials. Thus, these photoexcited catalysts can be used to generate free radicals from unactivated carbon-halogen bonds. The goal of this research program is to develop new coinage metal-catalyzed cyclization and photoredox transformations of general applicability for the synthesis of complex natural products.

开发新的碳-碳键合成方法对于高效合成在医学和材料科学中具有重要应用的分子具有至关重要的意义。大多数构建碳-碳键的传统化学反应具有较差的原子经济性，即试剂的数量与产生的所有产物的数量不相等，从而导致原子的浪费。在日益强调可持续性和环境问题的情况下，对有效和尽量减少废物的过程的需要变得越来越重要。过渡金属均相催化已成为有机化学研究的重要领域之一。近年来，铸造金属的均相催化作用受到了科学界的广泛关注。例如，在许多其他官能团存在的情况下，Au（I/III）盐对炔和烯的高亲和力，加上其稳定阳离子电荷的能力，为发现新的和有用的反应提供了巨大的机会。此外，磷二聚体金配合物具有高能量、长寿命的激发态和较强的还原势，可以用作光催化剂。因此，这些光激发催化剂可用于从未活化的碳-卤素键生成自由基。本研究计划的目标是开发新的金属催化环化和光氧化还原转化，普遍适用于复杂天然产物的合成。