Development of Novel Chiral Phosphines for Asymmetric Transition Metal Catalysis

膦配体是调节过渡金属催化活性的重要配体之一。手性膦在许多重要的过渡金属催化反应中被广泛用于诱导对映体选择性的控制。本项目将研究手性膦的合成和评价，这些膦具有额外的功能，可以与底物进行有吸引力的非共价相互作用。我们特别感兴趣的是研究与Buchwald型配体相关的配体，并且最近成功地进行了选择性交叉偶联以形成联苯酚（J. Am.化学会，2022，144，15026）。该项目将扩展这项工作，以靶向改性配体支架，以更广泛地应用于其他具有挑战性的对映选择性转化，包括钯催化剂和其他金属。

Phosphines are one of the most important ligand types for tuning the reactivity of transition metals that are used in catalysis. Chiral phosphines are used extensively for inducing control of enantioselectivity in a wide range of important transition metal-catalysed transformations. This project will investigate the synthesis and evaluation of chiral phosphines that possess additional functionality with which to engage in attractive non-covalent interactions with the substrate. We are particularly interesting in investigating such ligands that are related to Buchwald-type ligands and have had recent success for atroposelective cross-coupling to form biphenols (J. Am. Chem. Soc., 2022, 144, 15026). This project will expand on this work to target modified ligand scaffolds to apply more broadly to other challenging enantioselective transformations, both with palladium catalysts as well as other metals.