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

发展形成碳-碳键的新的合成方法对于有效地合成在医学和材料科学中具有重要应用的分子是至关重要的。传统的构建碳-碳键的化学反应大多具有较差的原子经济性，即试剂的量不等于所有产物的量，从而导致原子的浪费。随着人们对可持续性和环境问题的日益重视，对高效和最大限度减少浪费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，铸币金属的均相催化受到了科学界的极大关注。例如，在存在许多其他官能团的情况下，Au(I/III)盐对炔烃和烯的高亲和力，加上其稳定阳离子电荷的能力，为发现新颖和有用的反应提供了巨大的机会。此外，亚膦二聚金络合物具有高能、长寿命的激发态和较强的还原电势，可作为光催化剂。因此，这些光激发催化剂可以用来从未活化的碳-卤素键生成自由基。本研究的目标是开发具有普遍适用性的新型金属催化环化和光氧化还原反应，用于合成复杂的天然产物。

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.