7660-85-7Relevant academic research and scientific papers
Versatile Visible-Light-Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
Arockiam, Percia Beatrice,Lennert, Ulrich,Graf, Christina,Rothfelder, Robin,Scott, Daniel J.,Fischer, Tillmann G.,Zeitler, Kirsten,Wolf, Robert
supporting information, p. 16374 - 16382 (2020/11/03)
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 (P4) directly into symmetrical aryl phosphines and phosphonium salts in a single reaction step, which has previously only been possible using precious metal catalysis.
Decarboxylative Phosphine Synthesis: Insights into the Catalytic, Autocatalytic, and Inhibitory Roles of Additives and Intermediates
Jin, Shengfei,Haug, Graham C.,Nguyen, Vu T.,Flores-Hansen, Carsten,Arman, Hadi D.,Larionov, Oleg V.
, p. 9764 - 9774 (2019/10/14)
Phosphines are among the most widely used ligands, catalysts, and reagents. Current synthetic approaches to phosphines are dominated by nucleophilic displacement reactions with organometallic reagents. Here, we report a radical-based approach to phosphines that proceeds by a cross-electrophile coupling of chlorophosphines and redox-active esters. The reaction allows for the synthesis of a broad range of substituted phosphines that were not readily attainable with the present methods. Our experimental and DFT computational studies also clarified the catalytic, autocatalytic, and inhibitory roles of additives and intermediates, as well as the mechanistic details of the photocatalytic and zinc-mediated redox modes that can have implications for the mechanistic interpretation of other cross-electrophile coupling reactions.
Synthesis of Cp*CH2PPh2 and its use as a ligand for the nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents
Uemura, Minoru,Yorimitsu, Hideki,Oshima, Koichiro
, p. 4726 - 4728 (2007/10/03)
A new ligand, Cp*CH2PPh2 (Cp* = 1,2,3,4,5-pentamethyl-2,4-cyclopentadienyl), was prepared, and was used as a ligand for nickel-catalysed cross-coupling reaction of alkyl halides with aryl Grignard reagents, which nickel-phosphine complexes had never made possible. The Royal Society of Chemistry.
