Arockiam Percia Beatrice, Lennert Ulrich, Graf Christina, Rothfelder Robin, Scott Daniel J, Fischer Tillmann G, Zeitler Kirsten, Wolf Robert
Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
Institute of Organic Chemistry, University of Leipzig, 04103, Leipzig, Germany.
Chemistry. 2020 Dec 9;26(69):16374-16382. doi: 10.1002/chem.202002646. Epub 2020 Oct 30.
Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition-metal catalysts. Mild, practical methods thus remain elusive, despite being of great current interest. Herein, we describe a visible-light-driven method to form these products from secondary and primary phosphines. Using an inexpensive organic photocatalyst and blue-light irradiation, arylphosphines can be both alkylated and arylated using commercially available organohalides. In addition, the same organocatalyst can be used to transform white phosphorus (P ) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
不对称取代的叔膦和季鏻盐在整个工业和学术界的应用中被广泛使用。尽管它们很重要，但合成此类化合物的传统方法通常需要苛刻的反应条件、起始原料的预官能团化、高灵敏度的有机金属试剂或昂贵的过渡金属催化剂。因此，尽管目前备受关注，但温和、实用的方法仍然难以实现。在此，我们描述了一种由仲膦和伯膦形成这些产物的可见光驱动方法。使用廉价的有机光催化剂和蓝光照射，芳基膦可以使用市售的有机卤化物进行烷基化和芳基化。此外，相同的有机催化剂可用于在单个反应步骤中将白磷（P₄）直接转化为对称芳基膦和鏻盐，而这在以前只有使用贵金属催化才能实现。
