Roediger Sven, Leutenegger Sebastian U, Morandi Bill
Laboratorium für Organische Chemie, ETH Zürich Vladimir-Prelog-Weg 3, HCI 8093 Zürich Switzerland
Chem Sci. 2022 Jun 14;13(26):7914-7919. doi: 10.1039/d2sc02496a. eCollection 2022 Jul 6.
We report a diversification strategy that enables the direct substituent exchange of tertiary phosphines. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a nickel-catalysed process to access alkylphosphine products a formal substitution at the phosphorus center. The reaction can be used to introduce a wide range of alkyl substituents into both mono- and bisphosphines. We also show that the alkylation and dearylation steps can be conducted in a one-pot sequence, enabling accelerated access to derivatives of the parent ligand. The phosphine products of the reaction are converted to air-stable borane adducts for isolation, and versatile derivatisation reactions of these adducts are demonstrated.
我们报道了一种能够实现叔膦直接取代基交换的多样化策略。通过膦的标准烷基化制备的烷基鏻盐，在镍催化的过程中被选择性地脱芳基化，以获得烷基膦产物——磷中心的形式取代。该反应可用于将多种烷基取代基引入单膦和双膦中。我们还表明，烷基化和脱芳基化步骤可以一锅法进行，从而能够加速获得母体配体的衍生物。反应得到的膦产物被转化为空气稳定的硼烷加合物用于分离，并展示了这些加合物的多种衍生化反应。
