163311-93-1Relevant articles and documents
Defying Stereotypes with Nanodiamonds: Stable Primary Diamondoid Phosphines
Moncea, Oana,Gunawan, Maria A.,Poinsot, Didier,Cattey, Hélène,Becker, Jonathan,Yurchenko, Raisa I.,Butova, Ekaterina D.,Hausmann, Heike,?ekutor, Marina,Fokin, Andrey A.,Hierso, Jean-Cyrille,Schreiner, Peter R.
, p. 8759 - 8769 (2016)
Direct unequal C-H bond difunctionalization of phosphorylated diamantane was achieved in high yield from the corresponding phosphonates. Reduction of the functionalized phosphonates provides access to novel primary and secondary alkyl/aryl diamantane phos
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.
Reactions of 1- and 2-Halo and 1,2-Dichloroadamantanes with Nucleophiles by the SRN1 Mechanism
Santiago, Ana N.,Stahl, Adriana E.,Rodriguez, Gladis L.,Rossi, Roberto A.
, p. 4406 - 4411 (2007/10/03)
2-Bromoadamantane (2-BrAd) reacted in liquid ammonia under irradiation with diphenylphosphide (Ph2P-) ions whereas 2-chloroadamantane (2-ClAd) did not under the same experimental conditions. However, 2-ClAd yielded 2-(trimethylstannyl)adamantane in its photostimulated reaction with trimethylstannyl (Me3Sn-) ions. The compound 1-ClAd yielded the substitution product in a photostimulated slow reaction when the nucleophile is Ph2P- ion; the reaction occurs faster with the nucleophile Me3Sn- ion. All these reactions can be explained by the SRN1 mechanism as they did not occur in the dark and were inhibited by p-dinitrobenzene when photostimulated. In competition experiments, 1-haloadamantane showed more reactivity than 2-haloadamantane. Either with Ph2P- or Me3Sn- ions, 1-BrAd is 1.4 times more reactive than 2-BrAd while 1-ClAd is 12 times more reactive than 2-ClAd with Me3Sn- ions. In the photostimulated reaction of 1,2-dichloroadamantane (7) with Ph2P- the monosubstitution products 1-adamantyldiphenylphosphine (64%) and 2-adamantyldiphenylphosphine (15%) were formed, isolated as the oxides. From these results, it appears that when 7 receives an electron, the 1-position fragments ca. four times faster than the 2-position. The disubstitution product was not formed with Ph2P- ions, but when 7 reacted with a nucleophile having less steric bulk such as a Me3Sn- ion, the 2-chloro-1-(trimethylstannyl)-adamantane and the disubstitution product 1,2-bis(trimethylstannyl)adamantane were formed. The formation of these products is explained in terms of the different rates of the electron transfer reactions of the radical anion intermediates.
